Processes for preparing zincoaluminosilicates with aei, cha, and gme topologies and compositions derived therefrom

ABSTRACT

The present disclosure is directed to methods of producing zincoaluminosilicate structures with AEI, CHA, and GME topologies using organic structure directing agents (OSDAs), and the compositions and structures resulting from these methods.

CROSS REFERENCE TO RELATED APPLICATIONS

This applications claims priority to U. S. Patent Application Ser. No.62/119,945 filed Feb. 24, 2015 and U. S. Patent Application Ser. No.62/133,074 filed Mar. 13, 2015, the contents of which are incorporatedby reference herein in their entireties for all purposes.

TECHNICAL FIELD

The present disclosure is directed to methods of producingzincoaluminosilicate structures with AEI, CHA, and GME topologies usingorganic structure directing agents (OSDAs), and the compositions andstructures resulting from these methods.

BACKGROUND

The aluminosilicate version of the molecular sieve with the frameworktopology code AEI was first reported in 1997 and it was given the nameSSZ-39. The previous materials with the AEI framework features wereALPO-18 (an aluminophosphate) and SAPO-18 (a silicoaluminophosphates).The AEI framework describes a material that has 8-membered ring (MR)openings and constitutes a 3D channel (8×8×8) system with equal poresizes of 3.8×3.8 Å and medium size cages that can contain spheres up to7.3 A. Lately, there has been an increase of interest in 8MR systems forcatalysis and gas separations. Two very promising catalytic applicationsare the methanol (or oxygenates) to olefins conversion (MTO) and theselective catalytic reduction (SCR) of NO_(x) in flue and exhaust gases.Specific 8MR materials of interest for such applications have been foundwithin the CHA, LEV, AFX, KFI, RTH and AEI topologies. Morespecifically, Cu-exchanged AEI type materials, such as Cu-SAPO-18 andCu-SSZ-39, have been found to be very efficient and stable in the SCRreaction.

SAPO materials and zeolites only provide exchange sites for divalentions (such as Cu²⁺) when framework heteroatom (Al in the zeolite case,Si in the SAPO case) substitution is high and these sites are close toeach other. This can for instance occur in bridged substitution sites,as seen in FIG. 1(A) for zeolites or when the sites are close enough dueto the shape of the composite building unit of the framework, as seen inFIG. 1(B) for a d6r zeolite building block. A molecular sieve withdivalent species built in into a siliceous framework in a tetrahedralfashion ideally gives the framework a local charge deficit of -2. Thislocal charge deficit can be balanced by cationic species such as H⁺,Na⁺, Li⁺, et cetera but also by divalent cations such as Cu²⁺, Ca²⁺,Ni²⁺, etc. as shown in FIG. 1(C) for zincosilicates. The catalytic andgas separation properties of molecular sieves highly depend on the typeof exchanged cations and the framework sites they balance. For the SCRof NO_(x) with zeolites, it has been noted that only divalent cationicCu²⁺, ideally exchanged near two negative framework charges, are key inthe catalytic cycle. Over-exchanged samples, for instance when [Cu(OH)]⁺species are present near a negative framework charge, could be lessappealing. In most aluminosilicate materials, the amount of divalentexchange sites are thus limited and require the use of zeolites with alow Si/Al ratio. The introduction of Zn along with Al in suitedzeolites, creating zincoaluminosilicates, would therefore increase thenumber of (divalent) exchange sites. Moreover, active sites for sorptionand catalysis derived from cations exchanged on framework Zn, or theframework Zn site itself, could react differently compared to classicAl-based active sites.

However, the use of zincosilicate molecular sieves can often be limiteddue to their lower stability against hydrolysis or collapse, which isespecially striking compared to the high stability of silicate oraluminosilicate molecular sieves. Therefore, and for other reasons ofcatalytic nature, it is desirable to create zincoaluminosilicatematerials, rather than pure zincosilicates. Synthesizing such materialsis difficult and only very few have ever been reported. A notableexample is a VET analogue called SSZ-41 which can contain both Zn and Alin the framework. However, this material closely resembles the VPI-8material, which is a pure zincosilicate, due to its very low aluminumcontent. Other documented zincoaluminosilicates are found in MAZ, OFF,and FAU topologies but there, the proof of Zn incorporation is notunambiguous. Materials incorporating both Zn and Al in appropriateamounts are hard to make, especially since the presence of Zn insynthesis gels is known to either favor formation of (or direct to) onlya couple of frameworks (such as ANA and VET) or inhibit zeoliteformation entirely.

The present invention is directed to addressing at least some of theshortcomings of the existing art.

SUMMARY

The present invention is directed to the use of quarternary salts undercertain conditions to prepare zincoaluminosilicates with AEI, CHA, andGME topologies, and the novel materials derived from these processes.This disclosure presents a new synthetic approach towardszincoaluminosilicates and materials and process applications derivedfrom that approach.

Certain embodiments of the present invention include those processescomprising preparing a zincoaluminosilicate composition of an AEI or GMEtopology, each process comprising hydrothermally treating an aqueouscomposition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of AEI or GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

The quaternary piperidinium cation of Formula (I) is defined in variousembodiments in terms of sub-genera and specific quaternary piperidiniumcations. For example, in some embodiments, the quaternary piperidiniumcation is defined in terms of:

-   -   (a) structures of Formula (IA) or (IB):

-   -   (b) certain N,N-dialkyl-2,6-lupetidinium cation or an        N,N-dialkyl-3,5-lupetidinium cation:

-   -   (c) cis-N,N-dialkyl-3,5-lupetidinium cation,        trans-N,N-dialkyl-3,5-lupetidinium cation,        cis-N,N-dialkyl-2,6-lupetidinium cation,        trans-N,N-dialkyl-2,6-lupetidinium cation or a combination        thereof, and    -   (d) cis-N,N-dimethyl-3,5-lupetidinium cation,        trans-N,N-dimethyl-3,5-lupetidinium cation,        cis-N,N-dimethyl-2,6-lupetidinium cation,        trans-N,N-dimethyl-2,6-lupetidinium cation or a combination        thereof.

In general, the quaternary 3,5 piperidinium cations, or mixturescomprising these cations are preferred, particularly,cis-N,N-dialkyl-3,5-lupetidinium cation, orcis-N,N-dimethyl-3,5-lupetidinium cation, of mixtures comprising thesecations.

Other embodiments include those processes comprising preparing azincoaluminosilicate composition of CHA topology, each processcomprising hydrothermally treating an aqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof,

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of CHA topology;

wherein:

R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl; and whereinthe quaternary trialkyladamantyl- or trialkylbenzyl-ammonium cation hasan associated bromide, chloride, fluoride, iodide, or hydroxide anion.

The trialkyladamantylammonium cation of Formula (II) and substitutedtrialkylbenzylammonium cation of Formula (III) are also described incertain subgenera and specific compounds.

The nature of the sources of the various oxides and their ratio ranges,the nature of the mineralizing agent, and the hydrothermal heatingconditions are also disclosed as separate embodiments.

The products of the hydrothermal treating may be isolated and subjectsto one or more of further processing conditions, in some cases specificto the nature of the isolated solid's topology. Such treatments include:

(a) heating the isolated crystalline microporous zincoaluminosilicatesolids at a temperature in a range of from about 250° C. to about 600°C.;

(b) contacting the isolated crystalline microporous zincoaluminosilicatesolid with ozone or other oxidizing agent at a temperature in a range of100° C. to 200° C.; and

(c) heating the isolated crystalline microporous zincoaluminosilicatesolid at a temperature in a range of from about 200° C. to about 600° C.in either the absence or the presence of an alkali, alkaline earth,transition metal, rare earth metal, ammonium or alkylammonium salts;

in each case for a time sufficient to form a dehydrated or anOSDA-depleted crystalline microporous zincoaluminosilicate product.Certain subembodiments describe specific aspects of these treatments.

These dehydrated or OSDA-depleted crystalline microporouszincoaluminosilicate products may be further treated with an aqueousammonium or metal cation salt and/or with at least one type oftransition metal or transition metal oxide.

Various embodiments disclose the compositions prepared by any one of theprocesses embodiments. These include compositions which may be describedas:

(a) compositions comprising the aqueous compositions used in thehydrothermal treatments together with a compositionally consistentcrystalline microporous zincoaluminosilicate product, thecompositionally consistent crystalline microporous zincoaluminosilicateproducts containing the respective OSDAs used in their preparationoccluded in their pores;

(b) the isolated crystalline microporous zincoaluminosilicate productswhich contain the respective OSDAs used in their preparation occluded intheir pores; and

(c) the crystalline microporous zincoaluminosilicate products from whichthe OSDAs have been dehydrated or substantially depleted from theirpores and/or which have been post-treated to add salts, metals, or metaloxides into the pores of the crystalline microporouszincoaluminosilicate products.

While these compositions have been described and claimed in terms of theprocesses used to prepare them, other embodiments describe and claimthese compositions in terms which do not require these processlimitations. For example, certain embodiments disclose compositions ofcrystalline microporous zincoaluminosilicate solids of AEI, CHA, or GMEtopologies. In other embodiments, the zincoaluminosilicate solids aredescribed in terms of the ratios of the respective components. Forexample, in certain embodiments, the zincoaluminosilicate solids of AEIor GME topologies, whether containing the OSDA or not, have molar ratioof Si:Al in a range of from 3 to about 200 (or SiO₂/Al₂O₃ ratio of from6 to 400) and molar ratios of Si:Zn in a range from 5 to 50. In otherembodiments, the zincoaluminosilicate solid of CHA topologies have molarratio of Si:Al in a range of from 4 to 100 (or SiO₂/Al₂O₃ ratio from 8to 200) and a molar ratios of Si:Zn in a range from 5 to 50. Independentembodiments provide subsets of these ranges.

In other embodiments, the zincoaluminosilicate solids are described interms of certain physical characteristics of the zincoaluminosilicatesolids, for example with respect to XRD patterns, ²⁹Si MAS NMR spectra,and thermogravimetric analysis (TGA) data.

Other embodiments include the processes directed to a range of organictransformations catalyzed by catalysts comprising the crystallinemicroporous zincoaluminosilicates. Among these processes are thosedirected to reducing NOx in exhaust gases by catalytic reduction,converting methane via partial oxidation to methanol, and convertinglower alcohols and other oxygenates to at least one type of olefin.

These inventive zincoaluminosilicates are also useful as ion exchangemedia, and various embodiments consider such applications.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods of making and methods of using,processes, devices, and systems disclosed. In addition, the drawings arenot necessarily drawn to scale. In the drawings:

FIG. 1 shows some of the different molecular sieve exchange sitescreated by Al substitution in zeolites (A, bridged Al substitutions, andB, Al-substitutions close to each other in the d6r building block—oxygenatoms omitted for clarity) and Zn substitution in zincosilicates (C).

FIG. 2 shows the quaternized N,N-dimethyl-3,5-dimethylpiperidiniumhydroxide OSDA.

FIG. 3 shows PXRD traces of as-made AEI phases produced in differentgels according to Table 1. *GME impurity. Note that mdu182 is a purealuminosilicate AEI: SSZ-39.

FIG. 4 shows PXRD traces of Zn—Al-AEI material produced in synthesisMDU143 after various treatments.

FIG. 5 shows TGA analyses of MDU143-materials: as made, ozone-treatedand calcined.

FIG. 6 shows PXRD on samples after TGA analyses up to 900° C. of MDU147and three control SSZ-39-based samples.

FIG. 7 shows full overview of ²⁹Si MAS (Bloch Decay) NMR for a series oftreatments on Zn—Al-AEI (MDU143) compared to the calcined SSZ-39 sample(MDU182). Both 500 and 200 MHz spectrometers used, as indicated. This isthe origin of the slight contraction of the main two signals (forinstance visible when comparing calcined and ozone-treated Zn—Al-AEI).In the figure, Condition (a) is calcination at 580° C.; Condition (b) istreatment in 0.3 M HCl overnight at 60° C.; Condition (c) is treatingwith 0.01 M HCl, 4 hours at room temperature

FIG. 8 shows scaled and stacked ²⁹Si MAS (Bloch Decay) NMR spectra andcrucial overlays for some of the NMR spectra from FIG. 7.

FIG. 9 shows PXRD traces of as-made Zn—Al-CHA and Zn—Al-GME phasesproduced in different gels according to Table 1 and a aluminosilicateGME comparison

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to methods preparing microporouscrystalline zincoaluminosilicate compositions of AEI, CHA, and GMEtopologies using piperidinium based Organic Structure Directing Agents(OSDAs), and the compositions derived from these methods.

This disclosure describes the synthesis and properties of a novelmolecular sieve containing both Zn and Al as heteroatoms in thezeolite's framework (zincoaluminosilicates) The new material iscrystalline and isostructural with AlPO-18 and SSZ-39, as it has aframework with the AEI topology (framework code of the structurecommission of the International Zeolite Association). The synthesis ofzincoaluminosilicates with the GME and CHA topologies are also shown.

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, processes, conditions or parameters described or shown herein,and that the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe invention herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this specification, claims, anddrawings, it is recognized that the descriptions refer to compositionsand processes of making and using said compositions. That is, where thedisclosure describes or claims a feature or embodiment associated with acomposition or a method of making or using a composition, it isappreciated that such a description or claim is intended to extend thesefeatures or embodiment to embodiments in each of these contexts (i.e.,compositions, methods of making, and methods of using).

Terms

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method or process steps; (ii) “consisting of” excludes anyelement, step, or ingredient not specified in the claim; and (iii)“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention. Embodimentsdescribed in terms of the phrase “comprising” (or its equivalents), alsoprovide, as embodiments, those which are independently described interms of “consisting of” and “consisting essentially of” For thoseembodiments provided in terms of “consisting essentially of” the basicand novel characteristic(s) of a process is the ability to provide thenamed zincoaluminosilicate using the named OSDAs without additionalcomponents, even if such components are present.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can also beused in the practice or testing of the present invention, representativeillustrative methods and materials are described herein.

Unless otherwise stated, ratios or percentages are intended to refer tomole percent or atom percent, as appropriate.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

The terms “oxygenated hydrocarbons” or “oxygenates” as known in the artof hydrocarbon processing to refer to components which include alcohols,aldehydes, carboxylic acids, ethers, and/or ketones which are known tobe present in hydrocarbon streams or derived from biomass streams othersources (e.g. ethanol from fermenting sugar).

The terms “separating” or “separated” carry their ordinary meaning aswould be understood by the skilled artisan, insofar as they connotephysically partitioning or isolating the product material from otherstarting materials or co-products or side-products (impurities)associated with the reaction conditions yielding the material. As such,it infers that the skilled artisan at least recognizes the existence ofthe product and takes specific action to separate or isolate it fromstarting materials and/or side- or byproducts. Absolute purity is notrequired, though it is preferred.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of at leastsolvents or other impurities, such as starting materials, co-products,or byproducts. In some embodiments, the isolated crystalline materials,for example, may be considered isolated when separated from the reactionmixture giving rise to their preparation, from mixed phase co-products,or both. In some of these embodiments, for example, purezincoaluminosilicates (or structures containing incorporated OSDAs) canbe made directly from the described methods. In some cases, it may notbe possible to separate crystalline phases from one another, in whichcase, the term “isolated” can refer to separation from their sourcecompositions.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesembodiments where the circumstance occurs and instances where it doesnot. For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present. Similarly, the phrase “optionally isolated” means thatthe target material may or may not be separated from other materialsused or generated in the method, and, thus, the description includesseparate embodiments where the target molecule or other material isseparated and where the target material is not separated, such thatsubsequence steps are conducted on isolated or in situ generatedproduct.

The terms “method(s)” and “process(es)” are considered interchangeablewithin this disclosure.

As used herein, the term “crystalline microporous solids” or“crystalline microporous silicate or aluminosilicate solids,” sometimesreferred to as “molecular sieves,” are crystalline structures havingvery regular pore structures of molecular dimensions, i.e., under 2 nm.The term “molecular sieve” refers to the ability of the material toselectively sort molecules based primarily on a size exclusion process.The maximum size of the species that can enter the pores of acrystalline microporous solid is controlled by the dimensions of thechannels. These are conventionally defined by the ring size of theaperture, where, for example, the term “8-MR” or “8-membered ring”refers to a closed loop that is typically built from eight tetrahedrallycoordinated silicon (or aluminum) atoms and 8 oxygen atoms. These ringsare not necessarily symmetrical, due to a variety of effects includingstrain induced by the bonding between units that are needed to producethe overall structure, or coordination of some of the oxygen atoms ofthe rings to cations within the structure. The term “silicate” refers toany composition including silicate (or silicon oxide) within itsframework. It is a general term encompassing, for example, pure-silica(i.e., absent other detectable metal oxides within the framework),aluminosilicate, borosilicate, or titanosilicate structures. The term“zeolite” refers to an aluminosilicate composition that is a member ofthis family. The term “aluminosilicate” refers to any compositionincluding silicon and aluminum oxides within its framework. In somecases, either of these oxides may be substituted with other oxides.“Pure aluminosilicates” are those structures having no detectable othermetal oxides in the framework. As long as the framework contains siliconand aluminum oxides, these substituted derivatives fall under theumbrella of aluminosilicates. Similarly, the term “zincoaluminosilicate”refers to any composition including silicon, aluminum, and zinc oxideswithin its framework. Such zincoaluminosilicates may be“pure-zincoaluminosilicates (i.e., absent other detectable metal oxideswithin the framework) or optionally substituted. When described as“optionally substituted,” the respective framework may contain boron,gallium, hafnium, iron, tin, titanium, indium, vanadium, zirconium, orother atoms substituted for one or more of the aluminum, silicon, orzinc atoms not already present in in the framework.

The present disclosure describes and is intended to lay claim to methodsof making crystalline compositions, the compositions themselves, andmethods of using the crystalline zincoaluminosilicate compositionshaving an AEI, CHA, or GME framework. The structural features associatedwith the AEI, CHA, and GME topologies are well-understood by thoseskilled in the art and are summarized, for example, in the Database ofZeolite Structures, maintained by the International Zeolite Association(IZA-SC). The most recently available Database at the timing of thisdisclosure is incorporated by reference for its descriptions of thesetopologies. Also as described elsewhere as well, it should beappreciated that any embodied feature described for one of thesecategories (i.e., compositions and methods of making or using) isapplicable to all other categories.

Processes of Preparing Crystalline Compositions

Certain embodiments of the present invention include those processes forpreparing and using crystalline zincoaluminosilicate compositions havingan AEI, CHA, or GME framework. These include hydrothermally treatingspecific compositions to prepare certain compositions, isolating theresulting crystalline materials, further post-processing of theseisolated materials, and a range of catalytic reactions which use them.Other embodiments include the compositions derived from thesepreparatory processes. The disclosure also provide characterizations ofa range of associated compositions, which are independent of the meansof making them. While many of the aspects of the processes for preparingthe AEI-, CHA-, and GME-type share common features, as to the processesusing them, there are distinctions. For the sake of clarity, thesedistinctions will be discussed separately.

AEI and GME Topologies

Certain embodiments involve those process for preparing azincoaluminosilicate composition having an AEI or GME topology, eachprocess comprising hydrothermally treating an aqueous compositioncomprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of AEI or GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

The counterion to the cationic organic structure directing agent mixturein Formula (I) (and in Formulae (II) and (III) discussed elsewhere) isgenerally a bromide, chloride, fluoride, iodide, or hydroxide ion, butthe OSDA may be added also to the composition as an acetate, nitrate, orsulfate. In some embodiments, the quaternary piperidinium cation has anassociated fluoride or hydroxide ion preferably substantially free ofother halide counterions. In separate embodiments, the associated anionis hydroxide.

It should be appreciated that the instant invention provides that thequaternary piperidinium cation may comprise one or more stereoisomers ofthe same structural compound or two or more different compounds,selected from these options. For the sake of brevity, reference to anisomer by individual digits is intended to refer to that isomersubstituted in that position. For example, the “2,6 isomer” refers to anisomer containing an alkyl substituent only in the R² and R⁶ positions;a “3,5 isomer” refers to an isomer containing an alkyl substituent onlyin the R³ and R⁵ positions.

Reference to “isomers” in Formula (I) (and Formula (IA) and (IB)discussed elsewhere) refers to both structural and stereochemicalisomers of the quaternary piperidinium cation. That is, reference to twoor more isomers may encompass multiple structural isomers (e.g.,individual mono-alkyl compounds substituted in the 2, 3, 4, 5, or 6positions, or di-alkyl compounds substituted in the 2,3 and 2,4 and 2,5and 2,6, and 3,4 and 3,5, and 4,5 positions, or combinations thereof).In some cases, these may include mixtures of homologs (e.g., where R² ismethyl and R⁶ is ethyl), stereoisomers of the same structural isomer(e.g., cis-2-methyl/6-methyl and trans-2-methyl/6-methyl), orcombinations of both (e.g., cis-2-methyl/6-methyl andtrans-2-methyl/6-ethyl).

For example, referring to the structure of Formula (I), options for thequaternary piperidinium cations include those where R², R³, R⁴, R⁵, andR⁶ are individually and independently methyl, ethyl, n-propyl, oriso-propyl, independent of stereochemistry. In separate embodiments, thecarbon skeleton of piperidinium cation may be di-, tri-, tetra-, orpenta-substituted with any of these C₁₋₃ alkyl groups, independent ofstereochemistry.

The piperidine frameworks which derive the quaternary piperidiniumcations may be conveniently derived from the hydrogenation of di-, tri,or tetraalkyl pyridine, via the intermediary formation of thecorresponding di-, tri, or tetraalkyl piperidinium precursors, forexample using Pt/H₂ or Raney Nickel catalysts. Given the availability ofsuch pyridine precursors, in some embodiments, dialkyl piperidiniumframeworks are conveniently obtained by such processes, especially, forexample, where R³ and R⁵ are alkyl, preferably ethyl or methyl, morepreferably methyl or where R² and R⁶ are alkyl, preferably ethyl ormethyl, more preferably methyl. In the former case, where R³ and R⁵ aremethyl and R², R⁴, and R⁶ are H, the structures are known as3,5-lupetidinium cations. In the latter case, where R² and R⁶ are methyland R³, R⁴, and R⁵ are H, the structures are known as 2,6-lupetidiniumcations.

R^(A) and R^(B) are defined as being independently a C₁₋₃ alkyl, ortogether with the N to which they are bound form a 5 or 6 memberedsaturated or unsaturated ring. As such, in some embodiments, R^(A) andR^(B) are independently methyl, ethyl, n-propyl, or iso-propyl. In otherembodiments, R^(A) and R^(B), together with the N to which they arebound, form a 5 or 6 membered saturated or unsaturated ring. Forexample, these may include structures described as a spiro-pyrrolidiniummoiety, also described as a 5-azonia-spiro[4,5] decane:

or a spiro-piperidinium moiety, also described as a6-azonia-spiro[4,5]undecane:

or a spiro-2,5-dihydro-1H-pyrrolium moiety, also described as a5-azonia-spiro[4,5]dec-2-ene:

Again, in certain embodiments of these structures, the 2,6 positions(i.e., R² and R⁶) are alkyl, preferably ethyl or methyl, more preferablymethyl, the remaining positions being H. In other embodiments, the 3,5positions (i.e., R³ and R⁵) are alkyl, preferably ethyl or methyl, morepreferably methyl, the remaining positions being H.

The use of isomeric mixtures of these quaternary piperidinium cations toprepare aluminosilicate (but not zincoaluminosilicate) frameworks of AEItopology, and their use at catalysts in certain organic transformationhave recently been disclosed by the present inventors. See U.S. patentapplication Ser. No. 14/929,571, filed Jan. 26, 2016, which isincorporated by reference herein in its entirety for all purposes.

In some embodiments, the OSDA used in these processes comprises at leastone isomer of the quaternary piperidinium cation of Formula (IA) or(TB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some embodiments, the quaternary piperidinium cation of Formula (I)is or comprises an N,N-dialkyl-2,6-lupetidinium cation or anN,N-dialkyl-3,5-lupetidinium cation:

where R^(A) and R^(B) are C₁₋₃ alkyl, preferable methyl. In separateindependent embodiments, the quaternary piperidinium cation of Formula(I) is or comprises an N,N-dialkyl-2,6-lupetidinium cation or anN,N-dialkyl-3,5-lupetidinium cation.

In related embodiments, the quaternary piperidinium cation of Formula(I) is an N,N-dimethyl-3,5-lupetidinium cation,N,N-dimethyl-2,6-lupetidinium cation, N,N-diethyl-3,5-lupetidiniumcation, N,N-diethyl-2,6-lupetidinium cation, a6,10-dimethyl-5-azonia-spiro[4.5]decane, a1,5-dimethyl-6-azonia-spiro[5. 5]undecane, a7,9-dimethyl-5-azonia-spiro[4.5]decane, a2,4-dimethyl-6-azonia-spiro[5.5] undecane, or a combination thereof.

Still further embodiments include those where the quaternarypiperidinium cation of Formula (I) is or comprisescis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Including those wherein R^(A) and R^(B) are both methyl.

In other embodiments, the quaternary piperidinium cation of Formula (I)comprise a mixture of cis-N,N-dimethyl-3,5-lupetidinium cation andtrans-N,N-dimethyl-3,5-lupetidinium cation, a mixture ofcis-N,N-dimethyl-3,5-lupetidinium cation andtrans-N,N-dimethyl-3,5-lupetidinium cation, or a combination thereof.

In some embodiments, the ratios of cis and trans in these di-substitutedmaterials may range from about 95% cis/5% trans to about 0% cis/100%trans. In other embodiments, the at least two isomers of the quaternarypiperidinium cation of Formula (I) comprise a mixture ofcis-N,N-dimethyl-3,5-lupetidinium cation andtrans-N,N-dimethyl-3,5-lupetidinium cation in a mole ratio of about 99%cis/1% trans to about 0% cis/100% trans. Other embodiments provide thatthese ratios range from about 98:2 to 95:5, from about 95:5 to 90:10,from 90:10 to 80:20, from 80:20 to 70:30, from 70:30 to 60:40, from60:40 to 50:50, 50:50 to 40:60, from 40:60 to 30:70, from 30:70 to20:80, from 20:80 to 10:90, from 10:90 to 0:100, from 95:5 to 75:25,from 75:25 to 50:50, from 50:50 to 25:75, from 25:75 to 5:100, or anycombination of two or more of these ranges, including overlappingranges, for example from 90:10 to 75:25. In each case, the ratios aremole% cis/mol % trans. As described elsewhere,cis-N,N-dimethyl-3,5-lupetidinium cations, or mixtures containingpredominantly cis-N,N-dimethyl-3,5-lupetidinium cations are preferred.

CHA Topologies

Certain other embodiments involve those process for preparing azincoaluminosilicate composition having a CHA topology, each processcomprising hydrothermally treating an aqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of CHA topology;

wherein:

R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl.

Each of the trialkyladamantylammonium cation or optionally substitutedtrialkylbenzylammonium cation of Formulae (II) and (III), respectivelyare considered independent embodiments. The phenyl group of thetrialkylbenzylammonium cation may be optionally substituted withindependently one to three fluoro or optionally fluorinated orperfluorinated C₁₋₃ alkyl groups. In this context, the term optionallyfluorinated or perfluorinated C₁₋₃ alkyl groups refers to—CH_(n)F_(3-n)(methyl, n=0 to 3), —C₂H_(n)F_(5-n) (ethyl, n=0 to 5), and—C₃H_(n)F_(7-n) (propyl and isopropyl, n=0 to 7).

In certain of these embodiments, this phenyl group is unsubstituted.

Additional embodiments of these processes include the use of thecompounds of Formula (II) or (III), wherein at least one of R⁷, R⁸, orR⁹ is methyl or ethyl. In certain embodiments, at least one of R⁷, R⁸,or R⁹ is methyl. In other embodiment, R⁷, R⁸, and R⁹ are methyl.

In certain embodiments, the quaternary trialkyladamantyl- ortrialkylbenzyl-ammonium cation has an associated bromide, chloride,fluoride, iodide, nitrate, or hydroxide anion. In other embodiments, thequaternary cation has an associated fluoride or hydroxide ion preferablysubstantially free of other halide counterions. In other Embodiments,the associated anion is hydroxide.

Other OSDAs known to be useful in the formation of CHA-type materialinclude:

Having now discovered the process conditions capable of producingzincoaluminosilicates having a CHA topologies, it is possible or likelythat these OSDAs may be operable under the same conditions. Accordingly,the use of these OSDAs under the process conditions described here forthe formation of zincoaluminosilicates having a CHA topologies are alsoconsidered embodiments of the present invention

Further Aspects of Processing—Characteristics of the Ingredients andProcessing Conditions.

As described above, the hydrothermal processes for preparing thecrystalline microporous zincoaluminosilicate solid of AEI, CHA, or GMEtopology require, inter alia:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof,

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide.

The processes comprise composition having at least a source of siliconoxide, a source of aluminum oxide, and a source of zinc oxide. That is,in certain subsets of these embodiments, the composition is absent anysource of one or more of boron oxide, gallium oxide, germanium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, or zirconium oxide.

In some embodiments, the sources of aluminum oxide, silicon oxide, zincoxide, or optional source of boron oxide, gallium oxide, germaniumoxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indiumoxide, vanadium oxide, zirconium oxide, or combination or mixturethereof comprises an alkoxide, hydroxide, oxide, mixed metal oxide, orcombination thereof.

The processes are described thus far in terms of “a source of a siliconoxide, and optionally a source of germanium oxide or combinationthereof” The use of a source of silicon oxide, germanium oxide, and anycombination thereof represent individual and independent embodiments.The presence of a source of silicon oxide, either by itself or incombination with sources of germanium oxide is preferred. In someembodiments, the source of silicon oxide may comprise amorphous silica,an aluminosilicate, a zincoaluminosilicate, zincosilicate, a silicate,silica hydrogel, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicate, a silica hydroxide, a silicon alkoxide, orcombination thereof. Sodium silicate or tetraorthosilicates arepreferred sources.

The source of aluminum oxide is or comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, an aluminum siloxide, analuminosilicate, a zincoaluminosilicate, zincoaluminate or combinationthereof. In some embodiments, a mesoporous or zeolite aluminosilicatematerial may be used as a source of both aluminum oxide and siliconoxide. For example, FAU type zeolites serve as useful precursors.

The source of zinc oxide is or comprises a zinc(II) dicarboxylate,zinc(II) halide, zinc(II) hydroxide, zinc(II)oxide, zinc(II)nitrate,zincosilicate, zincoaluminate or zincoaluminosilicate.

As should be apparent, in some embodiments, the sources of siliconoxide, aluminum oxide, and zinc oxide may derive from common sources,for example, an aluminosilicate, a zincoaluminate, a zincosilicate, or azincoaluminosilicate. Given the novelty of the zincoaluminosilicatecompositions described in this disclosure, it should be appreciated thatin such embodiments, the zincosilicate, zincoaluminate orzincoaluminosilicate may be of a topology or composition different thanthe topology or composition of the intended product (e.g., differentthan the AEI, CHA, or GME topology eventually prepared and/or isolated,for example, as a Zn—Al-containing siliceous FAU-zeolite source). Inother embodiments, the zincosilicate, zincoaluminate orzincoaluminosilicate is the same topology or composition as the topologyor composition of the intended product, for example, acting as seeds.

In some processes (and corresponding compositions), the source ofsilicon oxide is or comprises sodium silicate, the source of Al is orcomprises a FAU-zeolite, and the source of zinc oxide is or compriseszinc acetate. In related embodiments, the sources of the silicon oxide,zinc oxide, and aluminum oxide is or comprises a Zn—Al-containing FAUmolecular sieve.

Thus far, the processes (and associated compositions) have beendescribed as in terms of the use or presence of a mineralizing agentSuch a mineralizing agent typically comprises an aqueous hydroxidederived from an alkali metal or alkaline earth metal hydroxide, therebyrendering these compositions alkaline. In certain aspects of thisembodiment, the alkali metal or alkaline earth metal hydroxide, mayinclude, for example, LiOH, NaOH, KOH, RbOH, CsOH, Mg(OH)₂, Ca(OH)₂,Sr(OH)₂, or Ba(OH)₂. LiOH, NaOH, or KOH appear to be preferred. In somecases, the pH of the water is in a range of from 7 to 7.5, from 7.5 to8, from 8 to 8.5, from 8.5 to 9, from 9 to 9.5, from 9.5 to 10, from 10to 11, from 11 to 12, from 12 to 13, from 13 to 14, or any combinationof two or more of these ranges, for example, at least 11. Under theseconditions, the oxide precursors can be expected to be at leastpartially hydrated or hydrolyzed to their hydroxide forms.

The processes and compositions may also be defined in terms of theratios of the individual ingredients. In certain embodiments, the molarratio of Al:Si is in a range of 0.005 to 0.2 (or the molar ratio ofSi:Al is in a range of from 5 to 200). In certain specific embodiments,the molar ratio of Al:Si is in a range of from 0.005 to 0.01, from 0.01to 0.02, from 0.02 to 0.03, from 0.03 to 0.05, from 0.05 to 0.06, from0.06 to 0.07, from 0.07 to 0.08, from 0.08 to 0.09, from 0.09 to 0.1,from 0.1 to 0.11, from 0.11 to 0.12, from 0.12 to 0.13, from 0.13 to0.14, from 0.14 to 0.15, from 0.15 to 0.16, from 0.16 to 0.17, from 0.17to 0.18, from 0.18 to 0.2, or any combination of two or more of theseranges, for example from 0.04 to 0.1. Again, the initial ratios ofprecursors will, at least in part, define the stoichiometries of thefinal crystalline materials. The person of skill in the art, using theteachings provided herein would be able to define the specific finalstoichiometries of interest without undue experimentation. It should beappreciated that while these stoichiometries are defined solely in termsof Si and Al, some portion or all of the Si content may be substitutedby Ge, and some portion of the Al may be substituted by B, Ga, Hf, Fe,Sn, Ti, In, V, or Zr.

In certain embodiments, the molar ratio of the respective OSDA (i.e., ofFormula (I), (II), or (III)):Si is in a range of 0.1 to 0.75. In certainspecific embodiments, the molar ratio of OSDA:Si is in a range of from0.1 to 0.12, from 0.12 to 0.14, from 0.14 to 0.16, from 0.16 to 0.18,from 0.18 to 0.2, from 0.2 to 0.22, from 0.22 to 0.24, from 0.24 to0.26, from 0.26 to 0.28, from 0.28 to 0.3, from 0.3 to 0.32, from 0.32to 0.34, from 0.34 to 0.36, from 0.36 to 0.38, from 0.38 to 0.4, from0.4 to 0.42, from 0.42 to 0.44, from 0.44 to 0.46, from 0.46 to 0.48,from 0.48 to 0.5, from 0.5 to 0.52, from 0.52 to 0.54, from 0.54 to0.56, from 0.56 to 0.58, from 0.58 to 0.6, from 0.6 to 0.63, from 0.63to 0.66, from 0.66 to 0.69, from 0.69 to 0.72, from 0.72 to 0.75, or anycombination of two or more of these ranges, for example from 0.1 to 0.5.Again, while described in terms of Si alone, in additional embodiments,the reference to Si may also refer to the presence of Si, Ge, or both,such that the named proportion of Si refers to the combined amounts ofSi and Ge.

In other embodiments, the molar ratio of water:Si is in a range of 5 to50. In certain specific embodiments, the molar ratio of water:Si is in arange of from 5 to 6, from 6 to 7, from 7 to 8, from 8 to 9, from 9 to10, from 10 to 11, from 11 to 12, from 12 to 13, from 13 to 14, from 14to 15, from 15 to 16, from 16 to 17, from 17 to 18, from 18 to 19, from19 to 20, from 20 to 22, from 22 to 24, from 24 to 26, from 26 to 28,from 28 to 30, from 30 to 32, from 32 to 34, from 34 to 36, from 36 to38, from 38 to 40, from 40 to 42, from 42 to 44, from 44 to 46, from 46to 48, from 48 to 50, or any combination of two or more of these ranges,for example from 10 to 50 or from 10 to 25. Again, while these ratiosare described in terms of Si alone, in additional embodiments, theseratios may also refer to the presence of Si, Ge, or both, such that thenamed proportion of Si refers to the combined amounts of Si and Ge.

In other embodiments, the molar ratio of total hydroxide:Si is in arange of 0.1 to 1.25. As used herein, the term “total hydroxide”includes the amount of hydroxide introduced with the OSDA and separatelyadded. In certain specific embodiments, the molar ratio of water:Si isin a range of from 0.1 to 0.15, from 0.15 to 0.2, from 0.2 to 0.25, from0.25 to 0.3, from 0.3 to 0.35, from 0.35 to 0.4, from 0.4 to 0.45, from0.45 to 0.5, from 0.5 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7, from0.7 to 0.75, from 0.75 to 0.8, from 0.8 to 0.85, from 0.85 to 0.9, from0.9 to 0.95, from 0.95 to 1, from 1 to 1.05, from 1.05 to 1.1, from 1.1to 1.15, from 1.15 to 1.2, from 1.2 to 1.25, or any combination of twoor more of these ranges, for example from 0.4 to 1. Again, while theseratios are described in terms of Si alone, in additional embodiments,these ratios may also refer to the presence of Si, Ge, or both, suchthat the named proportion of Si refers to the combined amounts of Si andGe.

In other embodiments, the molar ratio of Zn:Si is in a range of from0.01 to 0.2. In specific aspects of this, the molar ratio of Zn:Si is ina range of from 0.01 to 0.02, from 0.02 to 0.03, from 0.03 to 0.05, from0.05 to 0.06, from 0.06 to 0.07, from 0.07 to 0.08, from 0.08 to 0.09,from 0.09 to 0.1, from 0. 1 to 0.11, from 0.11 to 0.12, from 0.12 to0.13, from 0.13 to 0.14, from 0.14 to 0.15, from 0.15 to 0.16, from 0.16to 0.17, from 0.17 to 0.18, from 0.18 to 0.2, or any combination of twoor more of these ranges, for example from 0.01 to 0.1. Again, whilethese ratios are described in terms of Si alone, in additionalembodiments, these ratios may also refer to the presence of Si, Ge, orboth, such that the named proportion of Si refers to the combinedamounts of Si and Ge.

The hydrothermal treating is typically done at a temperature in a rangeof from about 100° C. to about 200° C. for a time effective forcrystallizing the respective crystalline microporouszincoaluminosilicate solid. Independent embodiments include those wherethe hydrothermal treating is done at at least one temperature in a rangeof from about 100° C. to 120° C., from 120° C. to 140° C., from 140° C.to 160° C., from 160° C. to 180° C., from 180° C. to 200° C., or anycombination of two or more of these ranges. In certain specificembodiments, the temperature is in a range of from 120° C. to 180° C.These ranges provide for convenient reaction times, though higher andlower temperatures may also be employed. In some embodiment, thesetemperatures are applied for times in a range of from 1 hour to 14 days.Again, longer or shorter times may also be employed. This hydrothermaltreating is also typically done in a sealed autoclave, at autogenouspressures. Some exemplary reaction conditions are provided in theExamples.

Once the initial zincoaluminosilicate solids are prepared, the processesinclude embodiments further comprising isolating these solids. Thesecrystalline solids may be removed from the reaction mixtures by anysuitable means (e.g., filtration, centrifugation, etc.), washed, anddried. Such drying may be done in air at temperatures ranging from 25°C. to about 200° C. Typically, such drying is done at a temperature ofabout 100° C.

These crystalline microporous zincoaluminosilicate solids may be furthermodified, for example, by incorporating metals with the pore structures,either before or after drying, for example by replacing some of thecations in the structures with additional metal cations using techniquesknown to be suitable for this purpose (e.g., ion exchange). Such cationscan include those of rare earth, Group 1, Group 2 and Group 8 metals,for example Li, K, Na, Ca, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pt, Pd, Re, Sn,Ti, V, W, Zn and their mixtures.

Where the isolated solid is a zincoaluminosilicate of AEI or CHAtopology, further processing of these materials, whether modified ornot, may comprise heating the isolated crystalline microporouszincoaluminosilicate solid at a temperature in a range of from about250° C. to about 600° C. to form an OSDA-depleted zincoaluminosilicateproduct. This calcining step may be carried out by holding thecrystalline microporous solid at at least one or more temperatures. Insome cases two or more temperatures, in a range of from 350° C. to 400°C., from 400° C. to 450° C., from 450° C. to 500° C., from 500° C. to550° C., from 550° C. to 600° C., or any combination of two or more ofthese ranges may be employed. In certain specific embodiments, where theproduct is a zincoaluminosilicate solid of GME topology, the temperaturerange is from about 250° C. to about 400° C. In either case, the heatingmay be done in an oxidizing atmosphere, such as air or oxygen, or in thepresence of other oxidizing agents. In other embodiments, the heating isdone in an inert atmosphere, such as argon or nitrogen.

In those embodiments where the processing involved heating, typicalheating rates include is 0.1° C. to 10° C. per minute and or 0.5° C. to5° C. per minute. Different heating rates may be employed depending onthe temperature range. Depending on the nature of the calciningatmosphere, the materials may be heated to the indicated temperaturesfor periods of time ranging from 1 to 60 hours or more, to produce acatalytically active product.

As used herein, the term “OSDA-depleted” (or composition having depletedOSDA) refers to a composition having a lesser content of OSDA after thetreatment than before. In preferred embodiments, substantially all(e.g., greater than 90, 95, 98, 99, or 99.5 wt %) or all of the OSDA isremoved by the treatment; in some embodiments, this can be confirmed bythe absence of a TGA endotherm associated with the removal of the OSDAwhen the product material is subject to TGA analysis or the absence orsubstantial absence of C or N in elemental analysis (prior to heating,expect composition to comprise C, N, O, Si, Al, H, and optionally Li,Na, K).

Further processing of these materials, whether modified or not, may alsocomprise contacting the isolated crystalline microporouszincoaluminosilicate solid with ozone or other oxidizing agent at atemperature in a range of 100° C. to 200° C. for a time sufficient toform an OSDA-depleted zincoaluminosilicate product. In certain of theseembodiments, the heating is done at a temperature of about 150° C. toform an OSDA-depleted product. The ozone-treatment can be carried out ina flow of ozone-containing oxygen (typically for 6 hours or more. butshorter could be feasible). Any oxidative environment treatmentsufficient to remove the OSDA can be used. Such environments, forexample, can involve the use of organic oxidizers (alkyl or arylperoxides or peracids) or inorganic peroxides (e.g., H₂O₂) (alkyl oraryl peroxides or peracids.

Where the isolated solid is a zincoaluminosilicate of GME topology,further processing of these materials, whether modified or not, may alsocomprise, heating the isolated crystalline microporouszincoaluminosilicate solid at a temperature in a range of from about200° C. to about 600° C. in the presence of an alkali, alkaline earth,transition metal, rare earth metal, ammonium or alkylammonium salts(anions including halide, preferable chloride, nitrate, sulfate,phosphate, carboxylate, or mixtures thereof) to form a dehydrated or anOSDA-depleted product. In certain of these embodiments, the heating isdone in the presence of NaCl or KCl. In certain exemplary embodiments,the heating is done at a temperature in a range of from 500 to 600° C.In exemplary embodiments, the heating is done in either an oxidizing orinert atmosphere.

Such use of salts is consistent with the disclosures provided in USPatent Appl. Publ. No. 2002/0119887 to Q. Huo and N. A. Stephenson. Forwater removal, the zincoaluminosilicate of GME topology is typicallyheated to 350° C. For substantial OSDA removal, temperatures up to 500°C. are typically employed. As described in Huo, the preferred saltsinclude alkali metal (Li, Na, K, Rb, Cs) halides (preferably CO;alkaline earth (Be, Mg, Ca, Sr, Be) nitrates or phosphates; aluminum,gallium, and indium carbonates; zinc sulfate; Ag, Cd borate or silicate;Ru, Rh, Pd, Pt, Au, or Hg carboxylates; La, Ce, Pr, Nd, Pm, or Smsulfonates; Eu, Gd alkoxide; R_(4-n)N⁺H_(n) phenolates, where R isalkyl, n=0-4—as described in Huo. In some cases, the excess salt orsalts can be removed, following calcination, by water (or other solvent)rinse or in a combination with ion-exchange and subsequent desolvation.

Once dehydrated or calcined, the dehydrated or OSDA-depleted crystallinemicroporous material may be treated with an aqueous ammonium or metalsalt or may be treated under conditions so as to incorporate at leastone type of alkaline earth metal or alkaline earth metal oxide or salt,or transition metal or transition metal oxide. In some embodiments, thesalt is a halide salt. Where the salt is an ammonium salt, the resultingzincoaluminosilicate contains the ammonium cation which, aftercalcination, decomposes to provide the protonated zincoaluminosilicate.In other embodiments, the metal salt comprises one or more of K⁺, Li⁺,Na⁺, Rb⁺, Cs⁺: Co²⁺, Ca²⁺, Mg²⁺, Sr²⁺; Ba²⁺; Ni²⁺; or Fe²⁺. In otherspecific embodiments, the metal cation salt is a copper salt, forexample, Schweizer's reagent (tetra-aminediaquacopper dihydroxide,[Cu(NH₃)₄(H₂O)₂](OH)₂]), copper(II) nitrate, copper (II) diacetate (orother dicarboxylate), or copper(II) carbonate.

The addition of a transition metal or transition metal oxide may beaccomplished, for example by chemical vapor deposition or chemicalprecipitation. As used herein, the term “transition metal” refers to anyelement in the d-block of the periodic table, which includes groups 3 to12 on the periodic table. In actual practice, the f-block lanthanide andactinide series are also considered transition metals and are called“inner transition metals. This definition of transition metals alsoencompasses Group 4 to Group 12 elements. In certain independentembodiments, the transition metal or transition metal oxide comprises anelement of Groups 6, 7, 8, 9, 10, 11, or 12. In other independentembodiments, the transition metal or transition metal oxide comprisesscandium, yttrium, tin, titanium, zirconium, vanadium, manganese,chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt,rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, ormixtures. Fe, Ru, OS, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixturesthereof are preferred.

Intermediate Reaction Compositions

As described herein, the as-formed and post-treated crystallinezincoaluminosilicate compositions themselves are within the scope of thepresent disclosure and are considered to be independent embodiments ofthe present invention. All of the descriptions used to describe thefeatures of the inventive processes are also considered to apply tothese compositions. In an abundance of caution, some of these arepresented here, but these descriptions should not be considered toexclude embodiments provided elsewhere.

Included in these embodiments are the compositions comprising theaqueous compositions used in the hydrothermal treatments together withthe respective crystalline microporous zincoaluminosilicate products,wherein the zincoaluminosilicate products contain the respective OSDAsused in their preparation occluded in their pores.

For example, in some embodiments, the composition comprises:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide, or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source zinc oxide;

(d) a mineralizing agent;

(e) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I) (or any ofthe embodied cations of Formula (I) described elsewhere in thisdisclosure); and

(f) a compositionally consistent crystalline microporouszincoaluminosilicate solid of an AEI or GME topology.

In other embodiments, such a composition comprises:

-   -   (a) a source of a silicon oxide, and optionally a source of        germanium oxide or combination thereof;    -   (b) a source of aluminum oxide, and optionally a source of boron        oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,        titanium oxide, indium oxide, vanadium oxide, zirconium oxide,        or combination or mixture thereof; and    -   (c) a source of a zinc oxide;    -   (d) a mineralizing agent; and    -   (e) an organic structure directing agent (OSDA) comprising a        trialkyladamantylammonium cation of Formula (II) or an        optionally substituted trialkylbenzylammonium cation of        Formula (III) (or any of the embodied cations of Formulae (II)        or (III) described elsewhere in this disclosure): and    -   (f) a compositionally consistent crystalline microporous        zincoaluminosilicate solid of an AEI or GME topology.

As used herein, the term “compositionally consistent” refers to acrystalline zincoaluminosilicate composition having a stoichiometryresulting from the crystallization of the sources of oxides in thepresence of the respective OSDAs; e.g., the OSDAs of Formula (I) for thezincoaluminosilicate having AEI or GME topologies or the OSDAs ofFormula (II) or (III) for the zincoaluminosilicate having CHA topology.In some of these embodiments, for example, this term reflects acomposition which is the result of at least a partial progression of thehydrothermal treating process used to prepare these materials.Typically, these compositionally consistent crystalline microporouszincoaluminosilicate solids contain, occluded in their pores, the OSDAsused to make them; i.e., the OSDAs present in the associated aqueouscompositions, and such is within the scope of the present disclosure. Inseparate embodiments, these compositionally consistent crystallinemicroporous zincoaluminosilicate solids may also be substantially freeof the OSDAs used in the aqueous media; in such embodiments, thezincoaluminosilicate may be used as seed material for thecrystallization.

These compositions may comprise any of the types and ratios ofingredients, and may exist at temperatures consistent with theprocessing conditions described above as useful for the hydrothermalprocessing. It should be appreciated that this disclosure captures eachand every of these permutations as separate embodiments, as if they wereseparately listed. In some embodiments, these compositions exist in theform of a gel.

Crystalline Microporous Compositions

In addition to the processing and process compositions, themicrocrystalline products resulting from the further processing of theinitially prepared materials are also considered within the scope of thepresent invention. Accordingly, in some embodiments, the variouscompositionally consistent crystalline microporous zincoaluminosilicatesolid of AEI, CHA, or GME topologies are isolated solids; i.e., theyexist in the absence of the aqueous hydrothermal treatment media used toproduce them. These isolated microporous zincoaluminosilicate solid ofAEI, CHA, or GME topologies may contain the any of the correspondingOSDAs described herein occluded in their pores—i.e., the OSDAs ofFormula (I) within the frameworks of the zincoaluminosilicates havingAEI or GME topologies or the OSDAs of Formula (II) or (III) within theframeworks of the zincoaluminosilicates having AEI or GME topologies—orthey may be devoid or substantially devoid of such organic materials(the terms “devoid” and “substantially devoid” being quantitativelyanalogous to the term “OSDA depleted”).

The presence of the OSDAs may be identified using, for example ¹³C NMRor any of the methods defined in the Examples. It is a particularfeature of the present invention that the cationic OSDAs retain theiroriginal structures, including their stereochemical conformations duringthe synthetic processes, these structures being compromised during thesubsequent calcinations.

More specifically, some embodiments provide crystalline microporouszincoaluminosilicate solids of GME or AEI topology having pores at leastsome of which are occluded with quaternary piperidinium cations ofFormula (I), in any of the embodiments described herein for thesecations. In other embodiments, the pores are substantiallyOSDA-depleted.

Such zincoaluminosilicate solids of GME or AEI topology may also bedescribed in terms of their Si:Al and Si:Zn molar ratios, as well astheir physical characteristics. In certain embodiments, the crystallinemicroporous zincoaluminosilicate solid having a GME or AEI topology arecharacterized as having a molar ratio of Si:Al in a range of from 3 toabout 200 (or SiO₂/Al₂O₃ ratio of from 6 to 400) and molar ratio ofSi:Zn in a range of from 5 to 50. Aspects of this embodiment includesthose where the molar ratio of Si:Al is in a range of from 3 to 3.2,from 3.2 to 3.4, from 3.4 to 3.6, from 3.6 to 3.8, from 3.8 to 4, from 4to 4.2, from 4.2 to 4.4, from 4.4 to 4.6, from 4.6 to 4.8, from 4.8 to5, from 5 to 5.2, from 5.2 to 5.4, from 5.4 to 5.6, from 5.6 to 5.8,from 5.8 to 6 from 6 to 6.4, from 6.4 to 6.8, from 6.8 to 7.2, from 7.2to 7.6, from 7.6 to 8, from 8 to 8.4, from 8.4 to 8.8, from 8.8 to 9.2,from 9.2 to 9.6 from 9.6 to 10, from 10 to 10.4, from 10.4 to 10.8, from10.8 to 11.2, from 11.2 to 11.6, from 11.6 to 12, from 12 to 12.4, from12.4 to 12.8, from 12.8 to 13.2, from 13.2 to 13.6, from 13.6 to 14,from 14 to 14.4, from 14.4 to 14.8, from 14.8 to 15.2, from 15.2 to15.4, from 15.5 to 15.8, from 15.8 to 16.2, from 16.2 to 16.6, from 16.6to 17, from 17 to 17.4, from 17.4 to 17.8, from 17.8 to 18.2, from 18.2to 18.6, from 18.6 to 19, from 19 to 19.4, from 19.4 to 19.8, from 19.8to 20, from 20 to 25, from 25 to 30, from 30 to 35, from 35 to 40, from40 to 45, from 45 to 50, from 50 to 60, from 60 to 70, from 70 to 80,from 80 to 90, from 90 to 100, from 100 to 120, from 120 to 140, from140 to 160, from 160 to 180, from 180 to 200, or any combination of twoor more of these ranges, including for example, from 3.6 to 15, from 5to 10, from 3 to 20, from 3 to 50. Other aspects include those where themolar ratio of Si:Zn is in a range of from 5 to 5.5, from 5.5 to 6, from6 to 6.5, from 6.5 to 7, from 7 to 7.5, from 7.5 to 8, from 8 to 8.5,from 8.5 to 9, from 9 to 9.5, from 9.5 to 10, from 10 to 11, from 11 to12, from 12 to 13, from 13 to 14, from 14 to 15, from 15 to 16, from 16to 17, from 17 to 18, from 18 to 19, from 19 to 20, from 20 to 21, from21 to 22, from 22 to 23, from 23 to 24, from 24 to 25, from 25 to 26,from 26 to 27, from 27 to 28, from 28 to 29, from 29 to 30, from 30 to34, from 34 to 38, from 38 to 42, from 42 to 46, from 46 to 50, or anycombination of two or more of these ranges, including for example, from8 to 26. Again, independent embodiments include the crystallinemicroporous zincoaluminosilicate solid having a GME or AEI topology andSi:Al and Si:Zn ratios when the pores are substantially depleted ofOSDA.

Other embodiments provide crystalline microporous zincoaluminosilicatesolids of CHA topology having pores at least some of which are occludedwith quaternary piperidinium cations of Formula (II) or (III), in any ofthe embodiments described herein for these cations. In otherembodiments, the pores are substantially OSDA-depleted.

Such zincoaluminosilicate solids of CHA topology may also be describedin terms of their Si:Al and Si:Zn ratios, as well as their physicalcharacteristics. In certain embodiments, the crystalline microporouszincoaluminosilicate solid having a CHA topology are characterized ashaving a molar ratio of Si:Al in a range of from 4 to 100 (or SiO₂/Al₂O₃ratio from 8 to 200) and a molar ratio of Si:Zn in a range from 5 to 50.Aspects of this embodiment includes those where the molar ratio of Si:Alis in a range of from 4 to 5, from 5 to 6, from 6 to 8, from 8 to 10, 10to 12, from 12 14, from 14 to 16, from 16 to 18, from 18 to 20, from 20to 22, from 22 to 24, from 24 to 26, from 26 to 28, from 28 to 30, from30 to 32, from 32 to 34, from 34 to 36, from 36 to 38, from 38 to 40,from 40 to 50, from 50 to 60, from 60 to 70, from 70 to 80, from 80 to90, from 90 to 100, or any combination of two or more of these ranges,including for example, from 4 to 12 or 6 to 10. Other aspects includethose where the molar ratio of Si:Zn is in a range of from 5 to 6, from6 to 7, from 7 to 8, from 8 to 9, from 9 to 10, from 10 to 12, from 12to 14, from 14 to 16, from 16 to 18, from 18 to 20, from 20 to 22, from22 to 24, from 24 to 26, from 26 to 28, from 28 to 30, from 30 to 32,from 32 to 34, from 34 to 36, from 36 to 38, from 38 to 40, from 40 to42, from 42 to 44, from 44 to 46, from 46 to 48, from 48 to 50, or anycombination of two or more of these ranges, including for example, from18 to 36 or from 20 to 30. Again, independent embodiments include thecrystalline microporous zincoaluminosilicate solid having a CHA topologyand Si:Al and Si:Zn ratios described here when the pores aresubstantially depleted of OSDA.

The crystalline microporous zincoaluminosilicate solids may alsocharacterized by their physical properties. In certain embodiments,these zincoaluminosilicate solid exhibit at least one of the following:

(a) an X-ray diffraction (XRD) pattern the same as or consistent withany one of those shown in FIG. 3 (Zn—Al-AEI), FIG. 4 (Zn—Al-AEI), orFIG. 9 (Zn—Al-GME and Zn—Al-CHA);

(b) an XRD pattern having at least the five major peaks substantially asprovided in Table 2 (see Example 2.1)

(c) an ²⁹Si MAS spectrum for having a plurality of chemical shifts ofabout −110.5, −105, −99.5 ppm downfield of a peak corresponding to andexternal standard of tetramethylsilane (for Zn—Al-AEI); or

(d) an Si MAS spectrum the same as or consistent with the one shown inFIG. 8 for Zn—Al-AEI.

Additional embodiments include those Zn—Al-AEI compositions exhibit (e)a thermogravimetric analysis (TGA) curve the same as or consistent withthe one shown in FIG. 5 (for Zn—Al-AEI) or (f); a thermogravimetricanalysis (TGA) curve indicative of a loss of 8 to 20 wt %.

The disclosed crystalline microporous zincoaluminosilicate compositionsinclude those which result from the post-treatment or further processingdescribed in the processing section. These include thosezincoaluminosilicates which are in their hydrogen forms or have cations,metals or metal oxides within their pore structures. Accordingly, incertain embodiments, the microporous zincoaluminosilicate solids havingAEI, CHA, and GME topologies, contain Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr,Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm,Sm, Eu, or R_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4 in at leastsome of their pores. In specific aspects of these embodiments, thesepores contain NaCl or KCl.

Additional embodiments include those crystalline microporouszincoaluminosilicate solids having AEI, CHA, and GME topologies, atleast some of whose pores transition metals, transition metal oxides, orsalts, for example scandium, yttrium, tin, titanium, zirconium,vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium,osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper,silver, gold, or mixtures thereof, each as a metal, oxide, or salt. Inone specific embodiment, the pores of the zincoaluminosilicate solidscontain copper, as cation, metal, oxide, or salt.

Use of the Inventive Compositions—Catalysis

The calcined crystalline microporous zincoaluminosilicate solids,calcined, doped, or treated with the catalysts described herein may alsobe used as catalysts for a variety of chemical reactions. The specificpore sizes of the AEI- and CHA-type frameworks makezincoaluminosilicates having these topologies particularly suited fortheir use in catalyzing reactions including carbonylating DME with CO atlow temperatures, reducing NOx with methane, reducing NOx with ammonia,MTO (methanol-to-olefin), oligomerizing alkenes, aminating loweralcohols, separating and sorbing lower alkanes, converting a loweralcohol (for example, methanol, ethanol, or propanol) or otheroxygenated hydrocarbon to produce an olefin products, reducing thecontent of an oxide of nitrogen contained in a gas stream in thepresence of oxygen, or separating nitrogen from a nitrogen-containinggas mixture. Such reactions may be catalyzed by contacting therespective feedstock with a catalyst comprising one or more of thecrystalline microporous zincoaluminosilicate solid having an AEI or CHAtopology under conditions sufficient to affect the named transformation.

Further, since the aluminosilicate version of AEI (SSZ-39), whenexchanged with Cu²⁺, is reported to have excellent catalytic propertiesfor deNO_(x) and a reported zincoaluminophosphate AEI material(ZnAPO-18) is reported to show good MTO activity, the presentzincoaluminosilicate are expected to show particular activity in theseapplications. Accordingly, some embodiments disclose processescomprising reducing NOx in exhaust gases by catalytic reduction (e.g.,with ammonia) or converting methane via partial oxidation to methanol,for examples with O₂, H₂O₂, or N₂O, with a catalyst comprising a copperexchanged crystalline microporous zincoaluminosilicate solid of AEI orCHA topology, under conditions sufficient to affect the namedtransformation. Additional embodiments include contacting methanol withthe crystalline microporous zincoaluminosilicate solid of AEI or CHAtopology under conditions sufficient to convert the methanol to at leastone type of olefin.

Catalysts comprising GME, having larger pore sizes, are capable ofcatalyzing all of the preceding reactions, as well as others, includingconverting methane via partial oxidation to methanol, convertingmethanol to at least one type of olefin, cracking, dehydrogenating,converting paraffins to aromatics, isomerizing xylenes,disproportionating toluene, alkylating aromatic hydrocarbons,hydrocracking a hydrocarbon, dewaxing a hydrocarbon feedstock,isomerizing an olefin, producing a higher molecular weight hydrocarbonfrom lower molecular weight hydrocarbon, or reforming a hydrocarbon.Such reactions may be catalyzed by contacting the respective feedstockwith a catalyst comprising at least the crystalline microporouszincoaluminosilicate solid having GME topology under conditionssufficient to affect the named transformation. Zincoaluminosilicatesolid having GME topology appear to be especially suitable for converingparaffins into aromatics (e.g., hexane to benzene) and for carbonylatingDME with CO at low temperatures. The GME framework topology is alsointeresting for applications in sorption and catalysis. Sorptionapplications could potentially be found in hydrocarbon separationprocesses and ion-exchange. Catalytic processes of interest include, butare not limited to, the aromatization of naphtha, the dehydrocyclizationof hexane, hydrocarbon isomerization and/or chlorination.

Specific conditions for many of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961, and U.S.Pat. No. 4,544,538, both of which are incorporated by reference hereinin its entirety for all purposes.

Depending upon the type of reaction which is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. As used herein, “predominantly in thehydrogen form” means that, after calcination (which may also includeexchange of the pre-calcined material with NH₄ ⁺ prior to calcination),at least 80% of the cation sites are occupied by hydrogen ions and/orrare earth ions.

Use of the Inventive Compositions—Ion Exchange

As described elsewhere herein, zincoaluminosilicates have an increasednumber of (divalent) exchange sites relative to aluminosilicates withthe same Si/Al ratios. These properties make these zincoaluminosilicatecompositions are expected to be useful in ion exchange applications.

The following listing of embodiments is intended to complement, ratherthan displace or supersede, any of the previous descriptions.

Embodiment 1. A process for preparing a zincoaluminosilicatecomposition, the process comprising hydrothermally treating an aqueouscomposition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of AEI or GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiment, the OSDA comprises at least oneisomer of the quaternary piperidinium cation of Formula (IA) or (IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.

Embodiment 2. The process of Embodiment 1, wherein the quaternarypiperidinium cation of Formula (I) is or comprises anN,N-dialkyl-2,6-lupetidinium cation or an N,N-dialkyl-3,5-lupetidiniumcation:

In separate Aspects of this Embodiment, the quaternary piperidiniumcation of Formula (I) is an N,N-dialkyl-2,6-lupetidinium cation. Inother Aspects, it is an N,N-dialkyl-3,5-lupetidinium cation.

Embodiment 3. The process of Embodiment 1 or 2, wherein the quaternarypiperidinium cation of Formula (I) is or comprisescis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 4. The process of Embodiment 2 or 3, wherein R^(A) and R^(B)are both methyl.

Embodiment 5. The process of any one of Embodiments 1 to 4, wherein thequaternary piperidinium cation has an associated fluoride or hydroxideion preferably substantially free of other halide counterions. Inseparate Aspects of this Embodiment, the associated anion is hydroxide.

Embodiment 6. A process for preparing a zincoaluminosilicate compositionof CHA topology, the process comprising hydrothermally treating anaqueous composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent; and

(e) an organic structure directing agent (OSDA) comprising atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of CHA topology;

wherein:

R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl; and whereinthe quaternary trialkyladamantyl- or trialkylbenzyl-ammonium cation hasan associated bromide, chloride, fluoride, iodide, nitrate or hydroxideanion. Each of the trialkyladamantylammonium cation of Formula (II) oran optionally substituted trialkylbenzylammonium cation of Formula (III)are considered independent Embodiments. In certain Aspects of thisEmbodiment, the phenyl group of the trialkylbenzylammonium cation may beoptionally substituted with independently one to three fluoro oroptionally fluorinated or perfluorinated C₁₋₃ alkyl groups.

Embodiment 7. The process of claim 6, wherein at least one of R⁷, R⁸, orR⁹ is methyl or ethyl. In certain Aspects of this Embodiment, at leastone of R⁷, R⁸, or R⁹ is methyl. In other Aspects of this Embodiment,each one of R⁷, R⁸, or R⁹ is methyl.

Embodiment 8. The process of any one of Embodiments 1 to 7, wherein thequaternary cation has an associated fluoride or hydroxide ion preferablysubstantially free of other halide counterions. In some Aspects of thisEmbodiment, the associated anion is hydroxide.

Embodiment 9. The process of any one of Embodiments 1 to 8, wherein thecomposition being hydrothermally treated is or comprises a source ofsilicon oxide, a source of aluminum oxide, and a source of zinc oxide.In other Aspects of this Embodiment, some of the sources of siliconoxide, aluminum oxide, and zinc oxide derive from common sources, forexample, an aluminosilicate, a zincoaluminate, a zincosilicate, or azincoaluminosilicate. In other Aspects of this Embodiment, thecomposition is absent any source of one or more of boron oxide, galliumoxide, germanium oxide, hafnium oxide, iron oxide, tin oxide, titaniumoxide, indium oxide, vanadium oxide, or zirconium oxide.

Embodiment 10. The process of any one of Embodiments 1 to 9, wherein thesource of aluminum oxide, silicon oxide, zinc oxide, or optional sourceof boron oxide, gallium oxide, germanium oxide, hafnium oxide, ironoxide, tin oxide, titanium oxide, indium oxide, vanadium oxide,zirconium oxide, or combination or mixture thereof comprises analkoxide, hydroxide, oxide, mixed metal oxide, or combination thereof.

Embodiment 11. The process of any one of Embodiments 1 to 10, whereinthe source of silicon oxide is or comprises an aluminosilicate, azincoaluminosilicate, zincosilicate a silicate, silica hydrogel, silicicacid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, asilica hydroxide or combination thereof. Given the novelty of thezincoaluminosilicate compositions described in this disclosure, itshould be appreciated that in certain Aspects of this Embodiment, thezincoaluminosilicate or zincosilicate is of a topology or compositiondifferent than the topology or composition of the intended product(e.g., different than the AEI, CHA, or GME topology eventually preparedand/or isolated). In other Aspects of this Embodiment, thezincoaluminosilicate or zincosilicate is the same topology orcomposition as the topology or composition of the intended product, forexample, acting as seeds.

Embodiment 12. The process of any one of Embodiments 1 to 11, whereinthe source of aluminum oxide is or comprises an alkoxide, hydroxide, oroxide of aluminum, a sodium aluminate, an aluminum siloxide, analuminosilicate, a zincoaluminosilicate, zincoaluminate or combinationthereof. Given the novelty of the zincoaluminosilicate compositionsdescribed in this disclosure, it should be appreciated that in certainAspects of this Embodiment, the zincoaluminosilicate or zincoaluminateis of a topology or composition different than the topology orcomposition of the intended product (e.g., different than the AEI, CHA,or GME topology eventually prepared and/or isolated, for example, as aFAU-zeolite source). In other Aspects of this Embodiment, thezincoaluminosilicate or zincoaluminate is the same topology orcomposition as the topology or composition of the intended product, forexample, acting as seeds.

Embodiment 13. The process of any one of Embodiments 1 to 12, whereinthe source of zinc oxide is or comprises a zinc(II) dicarboxylate,zinc(II) halide, zinc(II) hydroxide, zinc(II)oxide, zinc(II)nitrate,zincosilicate, zincoaluminate or zincoaluminosilicate. Given the noveltyof the zincoaluminosilicate compositions described in this disclosure,it should be appreciated that in certain Aspects of this Embodiment, thezincosilicate, zincoaluminate or zincoaluminosilicate is of a topologyor composition different than the topology or composition of theintended product (e.g., different than the AEI, CHA, or GME topologyeventually prepared and/or isolated, for example, as a Zn—Al-containingFAU-zeolite source). In other Aspects of this Embodiment, thezincosilicate, zincoaluminate or zincoaluminosilicate is the sametopology or composition as the topology or composition of the intendedproduct, for example, acting as seeds.

Embodiment 14. The process of any one of Embodiments 1 to 12, whereinthe source of silicon oxide is or comprises sodium silicate, the sourceof silicon and/or aluminum oxide is or comprises a FAU-zeolite, and thesource of zinc oxide is or comprises zinc acetate. In relatedembodiments, the sources of silicon oxide, zinc oxide, and aluminumoxide is or comprises a Zn—Al-containing FAU molecular sieve.

Embodiment 15. The process of any one of Embodiments 1 to 13, whereinthe mineralizing agent is or comprises an aqueous hydroxide. In certainAspects of this Embodiment, the hydroxide is an alkali metal or alkalineearth metal hydroxide, for example including LiOH, NaOH, KOH, RbOH,CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂.

Embodiment 16. The process of any one of Embodiments 1 to 14, whereinthe molar ratio of Al:Si is in a range of 0.005 to 0.2 (or the molarratio of Si:Al is in a range of from 5 to 200). In certain specificAspects of this Embodiment, the molar ratio of Al:Si is in a range offrom 0.04 to 0.1.

Embodiment 17. The process of any one of Embodiments 1 to 15, whereinthe molar ratio of OSDA:Si is in a range of 0.1 to 0.75. In certainspecific Aspects of this Embodiment, the molar ratio of OSDA:Si is in arange of from 0. 1 to 0.5.

Embodiment 18. The process of any one of Embodiments 1 to 16, whereinthe molar ratio of water:Si is in a range of 5 to 50. In certainspecific Aspects of this Embodiment, the molar ratio of water:Si is in arange of from 10 to 50 or from 10 to 25.

Embodiment 19. The process of any one of Embodiments 1 to 17, whereinthe molar ratio of total hydroxide:Si is in a range of 0.1 to 1.25. Incertain specific Aspects of this Embodiment, the molar ratio of totalhydroxide:Si is in a range of from 0.4 to 1. As used herein, the term“total hydroxide” includes the amount of hydroxide introduced with theOSDA and separately.

Embodiment 20. The process of any one of Embodiments 1 to 18, whereinthe molar ratio of Zn:Si is in a range of 0.01 to 0.2. In certainspecific Aspects of this Embodiment, the molar ratio of Zn:Si is in arange of from 0.01 to 0.1

Embodiment 21. The process of any one of Embodiments 1 to 19, whereinthe conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of AEI, CHA, or GME topology includetreatment of the hydrothermally treated composition at a temperature ina range of from 100° C. to 200° C. for a time effective forcrystallizing the crystalline microporous zincoaluminosilicate solid. Incertain specific Aspects of this Embodiment, the temperature is in arange of from 120° C. to 180° C. In certain specific Aspects of thisEmbodiment, this time is in a range of from 1 hour to 14 days. Incertain independent Aspects of this Embodiment, the times andtemperatures include ranges described elsewhere herein.

Embodiment 22. The process of any one of Embodiments 1 to 20, furthercomprising isolating the crystalline microporous zincoaluminosilicatesolid.

Embodiment 23. The process of Embodiment 21, further comprising heatingthe isolated crystalline microporous zincoaluminosilicate solid at atemperature in a range of from about 250° C. to about 600° C. to form anOSDA-depleted zincoaluminosilicate product. In certain specific Aspectsof this Embodiment, where the product is a zincoaluminosilicate solid ofGME topology, the temperature range is from about 250° C. to about 400°C. In certain independent Aspects of this Embodiment, the times andtemperatures include ranges described elsewhere herein. In certainindependent Aspects of this Embodiment, the heating is done in anoxidizing atmosphere, such as air or oxygen, or in the presence of otheroxidizing agents. In other Aspects, the heating is done in an inertatmosphere, such as argon or nitrogen.

Embodiment 24. The process of Embodiment 21, further comprisingcontacting the isolated crystalline microporous zincoaluminosilicatesolid with ozone or other oxidizing agent at a temperature in a range of100° C. to 200° C. for a time sufficient to form an OSDA-depletedzincoaluminosilicate product. In certain specific Aspects of thisEmbodiment, the heating is done at a temperature of about 150° C. toform an OSDA-depleted product.

Embodiment 25. The process of Embodiment 21, wherein the isolated solidis a zincoaluminosilicate of GME topology, the process furthercomprising heating the isolated crystalline microporouszincoaluminosilicate solid at a temperature in a range of from about200° C. to about 600° C. in the presence of an alkali, alkaline earth,transition metal, rare earth metal, ammonium or alkylammonium salts(anions including halide, preferable chloride, nitrate, sulfate,phosphate, carboxylate, or mixtures thereof) to form a dehydrated or anOSDA-depleted product. In certain Aspects of this Embodiment, theheating is done in the presence of NaC1 or KCl. Aspects of thisEmbodiment, the heating is done at a temperature in a range of from 500to 600° C. In still other Aspects of the Embodiment, the heating is donein either an oxidizing or inert atmosphere.

Embodiment 26. The process of any one of Embodiments 22 to 24, furthercomprising treating the dehydrated or OSDA-depleted product with anaqueous ammonium or metal cation salt. In some Aspects of thisEmbodiment, the salt is a halide salt. In some Aspects of thisEmbodiment, the metal salt comprises K⁺, Li⁺, Rb⁺, Cs⁺: Co²⁺, C²⁺, Mg²⁺,Sr²⁺; Ba²⁺; Ni²⁺; Fe²⁺. In other specific Aspects, the metal cation saltis a copper salt or complex, for example, Schweizer's reagent(tetraamminediaquacopper dihydroxide, [Cu(NH₃)₄(H₂O)₂](OH)₂]),copper(II) nitrate, copper(II) carbonate or copper(II) acetate.

Embodiment 27. The process of any one of Embodiments 22 to 24, furthercomprising treating at least some pores of the calcined crystallinemicroporous zincoaluminosilicate solid with at least one type oftransition metal or transition metal oxide. In certain Aspects of thisEmbodiment, the transition metal or transition metal oxide comprises aGroup 4 to Group 12 metal. In certain independent Aspects of thisEmbodiment, the transition metal or transition metal oxide comprises anelement of Groups 6, 7, 8, 9, 10, 11, or 12. In other independentAspects of this Embodiment, the transition metal or transition metaloxide comprises Fe, Ru, OS, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.

Embodiment 28. A composition prepared by any one of the processes ofEmbodiments 1 to 24.

Embodiment 29. A composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide, or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof;

(c) a source zinc oxide;

(d) a mineralizing agent;

(e) an organic structure directing agent (OSDA) comprising at least oneisomer of the quaternary piperidinium cation of Formula (I):

and

(f) a compositionally consistent crystalline microporouszincoaluminosilicate solid of an AEI or GME topology; wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiment, the OSDA comprises at least oneisomer of the quaternary piperidinium cation of Formula (IA) or (IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion. Eachof these cations is an independent Aspect of this Embodiment. In otherAspects of this Embodiment, the composition is absent any source ofaluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, or zirconiumoxide.

Embodiment 30. The composition of Embodiment 29, wherein the quaternarypiperidinium cation of Formula (I) is an N,N-dialkyl-2,6-lupetidiniumcation or N,N-dialkyl-3,5-lupetidinium cation:

Embodiment 31. The composition of Embodiment 29 or 30, wherein thequaternary piperidinium cation of Formula (I) iscis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Each of these cations is an independent Aspect of this Embodiment.

Embodiment 32. The composition of Embodiment 30 or 31, wherein R^(A) andR^(B) are both methyl.

Embodiment 33. A composition comprising:

(a) a source of a silicon oxide, and optionally a source of germaniumoxide or combination thereof;

(b) a source of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and

(c) a source of a zinc oxide;

(d) a mineralizing agent;

(e) an organic structure directing agent (OSDA) comprising atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

and

(f) a compositionally consistent crystalline microporouszincoaluminosilicate solid of a CHA topology;

wherein:

R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl; and wherein

the quaternary trialkyladamantyl- or trialkylbenzyl-ammonium cation hasan associated bromide, chloride, fluoride, iodide, nitrate, or hydroxideanion. Each of the trialkyladamantylammonium cation of Formula (II) oran optionally substituted trialkylbenzylammonium cation of Formula (III)are considered independent Embodiments. In certain Aspects of thisEmbodiment, the phenyl group of the trialkylbenzylammonium cation may beoptionally substituted with independently one to three fluoro oroptionally fluorinated or perfluorinated C₁₋₃ alkyl groups.

Embodiment 34. The composition of Embodiment 33, wherein at least one ofR⁷, R⁸, or R⁹ is methyl or ethyl. In certain Aspects of this Embodiment,at least one of R⁷, R⁸, or R⁹ is methyl. In other Aspects of thisEmbodiment, each one of R⁷, R⁸, or R⁹ is methyl.

Embodiment 35. The composition of any one of Embodiments 29 to 34,wherein the quaternary cation has an associated fluoride or hydroxideion preferably substantially free of other halide counterions. Inseparate Aspects of this Embodiment, the associated anion is hydroxide.

Embodiment 36. The composition of any one of Embodiments 29 to 35,comprising a source of silicon oxide, a source of aluminum oxide, and asource of zinc oxide. That is, the optionally sources of germaniumoxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide,titanium oxide, indium oxide, vanadium oxide, or zirconium oxide areabsent.

Embodiment 37. The composition of any one of Embodiments 29 to 36,wherein the source of aluminum oxide, boron oxide, gallium oxide,germanium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, silicon oxide, vanadium oxide, zirconium oxide, orcombination or mixture thereof is or comprises an alkoxide, hydroxide,oxide, or combination thereof of the corresponding metal.

Embodiment 38. The composition of any one of Embodiments 29 to 37,wherein the source of silicon oxide is or comprises an aluminosilicate,a zincoaluminosilicate, zincosilicate a silicate, silica hydrogel,silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate,a silica hydroxide, or combination thereof. Given the novelty of thezincoaluminosilicate compositions described in this disclosure, itshould be appreciated that in certain Aspects of this Embodiment, thezincoaluminosilicate or zincosilicate is of a topology or compositiondifferent than the topology or composition of the intended product(e.g., different than the AEI, CHA, or GME topology eventually preparedand/or isolated). In other Aspects of this Embodiment, thezincoaluminosilicate or zincosilicate is the same topology orcomposition as the topology or composition of the intended product, forexample, acting as seeds.

Embodiment 39. The composition of any one of Embodiments 29 to 38,wherein the source of aluminum oxide is or comprises an alkoxide,hydroxide, or oxide of aluminum, a sodium aluminate, an aluminumsiloxide, an aluminosilicate, a zincoaluminosilicate, zincoaluminate, orcombination thereof. Given the novelty of the zincoaluminosilicatecompositions described in this disclosure, it should be appreciated thatin certain Aspects of this Embodiment, the zincoaluminosilicate orzincoaluminate is of a topology or composition different than thetopology or composition of the intended product (e.g., different thanthe AEI, CHA, or GME topology eventually prepared and/or isolated, forexample, as a FAU-zeolite source). In other Aspects of this Embodiment,the zincoaluminosilicate or zincoaluminate is the same topology orcomposition as the topology or composition of the intended product, forexample, acting as seeds.

Embodiment 40. The composition of any one of Embodiments 22 to 39,wherein the source of zinc oxide is or comprises a zinc(II)dicarboxylate, zinc(II) halide, zinc(II) hydroxide, zinc(II)oxide,zinc(II)nitrate, zincosilicate, zincoaluminate or zincoaluminosilicate.Given the novelty of the zincoaluminosilicate compositions described inthis disclosure, it should be appreciated that in certain Aspects ofthis Embodiment, the zincosilicate, zincoaluminate orzincoaluminosilicate is of a topology or composition different than thetopology or composition of the intended product (e.g., different thanthe AEI, CHA, or GME topology eventually prepared and/or isolated, forexample, as a Zn—Al-containing FAU-zeolite source). In other Aspects ofthis Embodiment, the zincosilicate, zincoaluminate orzincoaluminosilicate is the same topology or composition as the topologyor composition of the intended product, for example, acting as seeds.

Embodiment 41. The composition of any one of Embodiments 29 to 40,wherein the source of silicon oxide is or comprises sodium silicate, thesource of Al is or comprises a FAU-zeolite, and the source of zinc oxideis or comprises zinc acetate. In related embodiments, the sources ofboth the zinc oxide and aluminum oxide is or comprises aZn—Al-containing FAU molecular sieve.

Embodiment 42. The composition of any one of Embodiments 29 to 41,wherein the mineralizing agent is or comprises aqueous hydroxide. Incertain Aspects of this Embodiment, the hydroxide is an alkali metal oralkaline earth metal hydroxide, for example including LiOH, NaOH, KOH,RbOH, CsOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂.

Embodiment 43. The composition of any one of Embodiments 29 to 42,wherein the molar ratio of Al:Si in the composition is in a range offrom 0.005 to 0.2 (or the molar ratio of Si:Al is in a range of from 5to 200). In certain specific Aspects of this Embodiment, the molar ratioof Al:Si is in a range of from 0.04 to 0.1.

Embodiment 44. The composition of any one of Embodiments 29 to 43,wherein the molar ratio of OSDA:Si in the composition is in a range offrom 0.1 to 0.75. In certain specific Aspects of this Embodiment, themolar ratio of OSDA:Si is in a range of from 0.1 to 0.5.

Embodiment 45. The composition of any one of Embodiments 29 to 44,wherein the molar ratio of water:Si in the composition is in a range offrom 5 to 50. In certain specific Aspects of this Embodiment, the molarratio of water:Si is in a range of from 10 to 50 or from 10 to 25.

Embodiment 46. The composition of any one of Embodiments 29 to 45,wherein the molar ratio of total hydroxide:Si is in a range of from 0.1to 1.25. In certain specific Aspects of this Embodiment, the molar ratioof total hydroxide:Si is in a range of from 0.4 to 1.

Embodiment 47. The composition of any one of Embodiments 29 to 46,wherein the molar ratio of Zn:Si in the composition is in a range offrom 0.01 to 0.2. In certain specific Aspects of this Embodiment, themolar ratio of Zn:Si is in a range of from 0.01 to 0.1

Embodiment 48. The composition of any one of Embodiments 29 to 47,wherein the composition exists at a temperature in a range of from 100°C. to 200° C. In certain specific Aspects of this Embodiment, thetemperature is in a range of from 120° C. to 180° C.

Embodiment 49. The composition of any one of Embodiments 29 to 48, thatis a gel.

Embodiment 50. A crystalline microporous zincoaluminosilicate solid ofGME or AEI topology having pores at least some of which are occludedwith quaternary piperidinium cations of Formula (I):

wherein

R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together with the Nto which they are bound form a 5 or 6 membered saturated or unsaturatedring; and

R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl.

In some Aspects of this Embodiment, the OSDA is or comprises at leastone isomer of the quaternary piperidinium cation of Formula (IA) or(IB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion. Incertain Aspects of this Embodiment, the composition is one characterizedas a CIT-9 composition as described herein.

Embodiment 51. The crystalline microporous zincoaluminosilicate solid ofEmbodiment 50, wherein the quaternary piperidinium cation of Formula (I)is or comprises an N,N-dialkyl-2,6-lupetidinium cation orNV,N-dialkyl-3,5-lupetidinium cation:

Embodiment 52. The crystalline microporous zincoaluminosilicate solid ofEmbodiment 49 or 50, wherein the quaternary piperidinium cation ofFormula (I) is or comprises cis-N,N-dialkyl-3,5-lupetidinium cation,trans-N,N-dialkyl-3,5-lupetidinium cation,cis-N,N-dialkyl-2,6-lupetidinium cation,trans-N,N-dialkyl-2,6-lupetidinium cation or a combination thereof:

Embodiment 53. The crystalline microporous zincoaluminosilicate solid ofEmbodiment 51 or 52, wherein R^(A)' and R^(B) are both methyl.

In certain Aspects, the crystalline microporous zincoaluminosilicatesolid of any one of Embodiments 50 to 53 (having a GME or AEI topology)having a molar ratio of Si:Al in a range of from 3 to about 20 (orSiO₂/Al₂O₃ ratio of from 6 to 40) and molar ratio of Si:Zn in a rangefrom 5 to 30. Independent Aspects of this Embodiment includes thosewhere the molar ratio of Si:Al in a range greater than 3.5 to about 15(or SiO₂/Al₂O₃ ratio greater than 7 to about 30) or from 5 to 10 and amolar ratio of Si:Zn in a range from 8 to 26. Independent Aspects ofthis Embodiment include those ranges described elsewhere herein. Incertain Aspects of this Embodiment, the crystalline microporouszincoaluminosilicate solid having a GME or AEI topology have these Si:Aland Si:Zn ratios when the pore are substantially depleted of OSDA.

Embodiment 54. A crystalline microporous zincoaluminosilicate solid ofCHA topology having pores at least some of which are occluded with atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

wherein:

R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl; and whereinthe quaternary trialkyladamantyl- or trialkylbenzyl-ammonium cation hasan associated bromide, chloride, fluoride, iodide, nitrate or hydroxideanion. The compositions containing the trialkyladamantylammonium cationof Formula (II) or an optionally substituted trialkylbenzylammoniumcation of Formula (III) are considered independent Embodiments. Incertain Aspects of this Embodiment, the phenyl group of thetrialkylbenzylammonium cation may be optionally substituted withindependently one to three fluoro or optionally fluorinated orperfluorinated C₁₋₃ alkyl groups.

Embodiment 55. The crystalline microporous zincoaluminosilicate solid ofEmbodiment 54, wherein at least one of R⁷, R⁸, or R⁹ is methyl or ethyl.In certain Aspects of this Embodiment, at least one of R⁷, R⁸, or R⁹ ismethyl. In other Aspects of this Embodiment, each one of R⁷, R⁸, or R⁹is methyl.

In certain Aspects, the crystalline microporous zincoaluminosilicatesolid of Embodiment 54 or 55 has a molar ratio of Si:Al in a range offrom 4 to 100 (or SiO₂/Al₂O₃ ratio from 8 to 200) and a molar ratio ofSi:Zn in a range from 10 to 50. Independent Aspects of this Embodimentinclude those where the molar ratio of Si:Al is in a range of from 4 to12 or 6 to 10 and where the molar ratio of Si:Zn is in a range of from18 to 36 or from 20 to 30 Independent Aspects of this Embodiment includethose where these ratios are those ranges described elsewhere herein.

Embodiment 56. A crystalline microporous zincoaluminosilicate solidexhibiting at least one of the following:

(a) an X-ray diffraction (XRD) pattern the same as or consistent withany one of those shown in FIG. 3 (Zn—Al-AEI), FIG. 4 (Zn—Al-AEI), orFIG. 9 (Zn—Al-GME and Zn—Al-CHA);

(b) an XRD pattern having at least the five major peaks substantially asprovided in Table 2.

(c) an ²⁹Si MAS spectrum for having a plurality of chemical shifts ofabout −110.5, −105, −99.5 ppm downfield of a peak corresponding to andexternal standard of tetramethylsilane (for Zn—Al-AEI); or

(d) an ²⁹Si MAS spectrum the same as or consistent with the one shown inFIG. 8 for Zn—Al-AEI.

Additional Aspects of these Embodiments include those compositions ofany one of Embodiments 50 to 53 which exhibit (e) a thermogravimetricanalysis (TGA) curve the same as or consistent with the one shown inFIG. 5 (for Zn—Al-AEI) or (f) ; a thermogravimetric analysis (TGA) curveindicative of a loss of 8 to 20 wt %. In certain Aspects of thisEmbodiment, the pore are substantially depleted of OSDA.

Embodiment 57. A crystalline microporous zincoaluminosilicate solidhaving a GME or AEI topology. In some Aspects of this Embodiment, thezincoaluminosilicate solid having a GME or AEI topology has a molarratio of Si:Al in a range of from 3 to 20 (or SiO₂/Al₂O₃ ratio of from 6to 40) and molar ratio of Si:Zn in a range from 5 to 30. IndependentAspects of this Embodiment include those ranges described elsewhereherein. In certain Aspects of this Embodiment, the pore aresubstantially depleted of OSDA.

Embodiment 58. A crystalline microporous zincoaluminosilicate solidhaving a CHA topology. In some Aspects of this Embodiment, thezincoaluminosilicate solid having a CHA topology has a molar ratio ofSi:Al in a range of from 4 to 100 (or SiO₂/Al₂O₃ ratio from 8 to 200)and molar ratio of Si:Zn in a range from 10 to 50. Independent Aspectsof this Embodiment include those where the molar ratio of Si:Al is in arange of from 4 to 12 or 6 to 10 and where the molar ratio of Si:Zn isin a range of from 18 to 36 or from 20 to 30 Independent Aspects of thisEmbodiment include those where these ratios are those ranges describedelsewhere herein. In certain Aspects of this Embodiment, the pore aresubstantially depleted of OSDA. In certain Aspects of this Embodiment,the crystalline microporous zincoaluminosilicate contains one or more ofthe OSDA described herein occluded within its pores. In other Aspects,the crystalline microporous zincoaluminosilicate is devoid orsubstantially devoid of such OSDAs.

Embodiment 59. The crystalline microporous zincoaluminosilicate solid ofany one of Embodiments 56 to 58, comprising pores, at least some ofwhich contain Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag,Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, orR_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4. In specific Aspects ofthis Embodiment, the pores contain NaCl or KCl.

Embodiment 60. The crystalline microporous zincoaluminosilicate solid ofany one of Embodiments claims 56 to 59, comprising pores, at least someof which contain scandium, yttrium, tin, titanium, zirconium, vanadium,manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium,cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver,gold, or mixtures thereof, each as a metal, oxide, or salt. In oneAspect of this Embodiment, the pores contain copper, as metal, oxide, orsalt.

Embodiment 61. A process comprising carbonylating DME with CO at lowtemperatures, reducing NOx with methane, reducing NOx with ammonia,converting methane via partial oxidation to methanol, convertingmethanol to at least one type of olefin, cracking, dehydrogenating,converting paraffins to aromatics, MTO, isomerizing xylenes,disproportionating toluene, alkylating aromatic hydrocarbons,oligomerizing alkenes, aminating lower alcohols, separating and sorbinglower alkanes, hydrocracking a hydrocarbon, dewaxing a hydrocarbonfeedstock, isomerizing an olefin, producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon, reforming ahydrocarbon, converting a lower alcohol or other oxygenated hydrocarbonto produce an olefin products, reducing the content of an oxide ofnitrogen contained in a gas stream in the presence of oxygen, orseparating nitrogen from a nitrogen-containing gas mixture by contactingthe respective feedstock with a catalyst comprising the crystallinemicroporous zincoaluminosilicate solid of any one of claims 56 to 60under conditions sufficient to affect the named transformation.

Embodiment 62. A process comprising reducing NOx in exhaust gases bycatalytic reduction (e.g., with ammonia) or converting methane viapartial oxidation to methanol, for examples with 0₂, H₂O₂, or N₂O, witha catalyst comprising a copper changed crystalline microporouszincoaluminosilicate solid of Embodiment 60, under conditions sufficientto affect the named transformation. In certain Aspects of thisEmbodiment, the catalyst comprises a zincoaluminosilicate of AEI or CHAor GME topology, whose pores contain exchanged copper.

Embodiment 63. A process comprising contacting methanol with thecrystalline microporous zincoaluminosilicate solid of Embodiment 58 to60 (as applied to Embodiment 58) under conditions sufficient to convertthe methanol to at least one type of olefin.

Embodiment 64. An ion exchange material comprising thezincoaluminosilicate of any one of claims 50 to 59.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees Celsius, pressure is ator near atmospheric.

Example 1 General Methods. Example 1.1 Materials and Methods.

cis-N,N-dimethyl-3,5-lupetidinium hydroxide (98/2 cis/trans) andtrimethyladamantylammonium hydroxide was acquired from SACHEM Inc.

²⁹Si NMR Bloch Decay (d1=60s) spectra were measured on a Bruker 500 MHzspectrometer in a 4 mm ZrO₂ rotor at a spinning rate of 8 kHz andreferenced externally versus tetramethylsilane. Additionally, a 200 MHzspectrometer was used with 7 mm rotors spinning at 4 kHz.

Thermogravimetric analysis (TGA) was performed on a Perkin Elmer STA6000 with a ramp of 10° C. min⁻¹ to 900° C. under air atmosphere.

SEM was performed on a ZEISS 1550 VP FESEM, equipped with an OxfordX-Max SDD X-ray Energy Dispersive Spectrometer (EDS) system fordetermining the Si/Al, Cu/Al, Na/Al and Si/Zn ratios of the samples.

All Powder X-ray diffraction (PXRD) characterization was conducted on aRigaku MiniFlex II with Cu K_(α) radiation.

Example 1.2 General Synthetic Methods

A general procedure for hydroxide syntheses was as follows. The OSDA inits hydroxide form was combined water in a 23 mL-Teflon Parr reactor.Then a silica source (N° Sodium silicate, PQ Corporation) andZn^(II)-acetate.dihydrate (Sigma Aldrich) were added as well. Finally,the aluminum source (CBV500=NH₄-FAU of Zeolyst) was added. The synthesiswas stirred until a homogenous gel was obtained. The Teflon Parr reactorwas then sealed and placed in a rotating or static oven at 140° C.Aliquots of the synthesis gels were taken periodically as follows:quenching the reactor in water, opening the reactor, stirring itscontents until homogeneous and finally, removing enough material forPXRD. After washing the aliquots once with water and once with acetone,they are left to dry in a 100° C. oven before PXRD measurement. Theyields were calculated as follows (without compensation for theintermediate aliquots): the final dry weight obtained after thoroughwashing of the finished syntheses with water and acetone and drying at100° C. is corrected with the weight loss of organic SDA and water inTGA up to 900° C. This corrected weight is assumed to be purezincoaluminosilicate and is divided by the maximum theoretical possiblezincoaluminosilicate formation from the input silica,alumina andzinc-oxide. The weight of inorganic cations present in the samples ishereby neglected. The reference aluminosilicate version of GME in FIG. 9was made in conditions identical to those of entry 7 in Table 1, butwith use of the classic Al source (NH₄-FAU) and thus without Znaddition.

The ozonolysis procedure for OSDA removal was carried out at 150° C. ina tube furnace by using a Longevity Resources ozone generator (settingat 2) and a oxygen gas flow of 200 cm³/min over 100-500 mg of as-madezeolite sample. Cu ion-exchanges were performed overnight on calcinedsamples in concentrated Schweizer's reagent solutions at roomtemperature under continuous stirring and at loadings of 1 g.100 mL⁻¹.This was repeated 3 times. After exchange, the samples were calcinedagain.

General calcination was performed in dry flowing air by heating to 150°C. at 1° C./min; holding for 3 h at 150° C., and then heated further to580° C. at 1° C./min and held for 6 h.

Example 2 Syntheses and Characterizations

Table 1 shows conditions for the preparation of a range ofzincoaluminosilicate compositions. A zincoaluminosilicate with the AEItopology, hereafter denoted Zn—Al-AEI, was made using a quaternizedN,N-dimethyl-3,5-dimethylpiperidine organic structure directing agent(OSDA) in combination with a Si source, Al-source, Zn-source, water and(sodium) hydroxide as a mineralizing agent. The OSDA is structurallyillustrated in FIG. 2. Representative reaction conditions which havebeen used to prepare Zn—Al-AEI are shown in Table 1, Entries 1-4, alongwith a control synthesis of a pure aluminosilicate AEI (SSZ-39), inentry 5. A CHA and GME recipe is found in entries 6 and 7, as discussedelsewhere herein.

TABLE 1 Typical Zn—Al-AEI syntheses reactions withN,N-dimethyl-3,5-dimethylpiperidinium hydroxide (98 cis/2% trans) as theOSDA (unless noted otherwise), NH4-FAU (CBV500, Si/Al 2.6) as aluminumsource, sodium silicates as silicon source and Zn-acetate for providingZn; unless otherwise noted. Gel composition relative to Si¹ (molarratios based on Si = 1) time Yield sample n° Al Zn OSDA H₂O OH⁻ (days)phase Si/Al Si/Zn (%) name 1 0.067 0.033 0.17 20.0 0.67 9 AEI 8.4 10.7n.d. MDU78 2 0.067 0.033 0.17 20.0 0.67 14 AEI 7.6 11.1 48 MDU147  3²0.066 0.032 0.17 20.0 0.67 14 AEI 7.7 11.3 56 MDU143  4³ 0.067 0.0330.17 20.0 0.67 21 AEI* n.d. n.d. 49 MDU223  5⁴ 0.033 / 0.14 20.7 0.71 3AEI⁵ 7.6 / 26 MDU182  6⁶ 0.067 0.033 0.17 20.1 0.67 7 CHA 8.4 26.2 31MDU148  7⁷ 0.055 0.017 0.18 20.3 0.72 4 GME 3.6 23.1 10 MDU215¹Synthesis at 140° C. in a rotating oven. OH— is the sum of inorganicand OSDA derived hydroxide contents. The inorganic derived hydroxide iscalculated from the presence of NaOH, which is calculated from the totalNa content, originating from NaOH addition and sodium silicate. The Znsource is Zn(II) acetate•dihydrate. The total OH— content is notcorrected for neutralization deriving from the acetate addition. n.d. =not determined. ²Repeat of entry 2, but at 2.5× the scale. ³Repeat ofentry 2, but syntheses at 5× the scale in a static oven. ⁴OSDA isN,N-dimethyl-2,6-dimethylpiperidinium hydroxide instead. ⁵Note that thephase is also AEI, but the material is a pure aluminosilicate, calledSSZ-39, see reference (2). ⁶OSDA is trimethyladamantylammonium hydroxideinstead.

⁷Instead of adding Zn-acetate in the gel, a different home-made FAUzeolite containing Zn, Si and Al was used as source for both Zn and Al(and partially Si). This Na-FAU was made along the recipe provided inHunsicker, R. A.; Klier, K.; Gaffney, T. S.; Kimer, J. G. Chem. Mater.2002, 14, 4807 and Chen, J.; Thomas J. M. J. Chem. Soc., Chem. Commun.1994, 603. and had Si/Al 3.2 and Si/Zn 10.2. *Presence of a smallimpurity, probably GME noted.

The syntheses in Table 1 (Entries 1 to 4) demonstrated that the methodis reproducible and that larger scale and static reactions are possible.The materials were obtained in modest yields (based on the maximumtheoretical silica, alumina and zinc-oxide formation) and with Si/Alratios of about 8 and Si/Zn ratios around 11. The SSZ-39 from entry 5had a similar Si/Al of 7.6.

One evidence of the synthesis of a new, Zn and Al containing siliceousAEI material can be found in the synthesis times. While normal SSZ-39synthesis in similar conditions lasts only three days; the synthesisconditions with Zn in the gel crystallized much more slowly. This couldbe an indication of either a Zn-acetate induced, slower formation ofregular SSZ-39 or the formation of a new Zn—Al-AEI material. In the caseof the former, Zn could be present in the solid sample as ZnO, causing abulk Si/Zn measure in EDS. To further corroborate that the latter washappening, viz. the formation of a new AEI material with both Zn and Alin a siliceous framework, extensive characterization and additionalarguments were gathered and shown as follows.

Example 2.1 Characterizations by Powder X-Ray Diffraction (PXRD)

Based on a comparison of the PXRD patterns obtained as a result of thesesyntheses (FIG. 3) with patterns provided in the literature (see, e.g.,IZA-Structure-Commission, Database of Zeolite Structures,http://izasc.biw.kuleuven.be/fmi/xsl/IZA-SC/ft.xsl, Accessed 23 Jan.2015; U.S. Pat. No. 5,958,370 (to Zones, et al.); and Wagner, P., etal., J. Am. Chem. Soc. 1999, 122, 263) it was clear that allzinc-containing phases produced in entries 1-4 of Table 1 possessed theAEI framework topology. See Table 2. The clean SSZ-39 (AEI) from MDU182(entry 5) presented a good comparison, as did the pattern of purezinc-oxide. Reflections of the latter were clearly not found in any ofthe Zn—Al-AEI samples and ruled out the formation of PXRD-visible ZnOnext to SSZ-39 in the Zn—Al-AEI syntheses.

TABLE 2 PXRD data for representative zincoaluminosilicates. Values in2θ. See also FIG. 3, FIG. 4, and FIG. 9. Zn—Al-AEI Zn—Al-GME Zn—Al-CHA 9.4 ± 0.2  7.4 ± 0.2  9.5 ± 0.2 10.5 ± 0.2 11.5 ± 0.2 14.0 ± 0.2 13.9 ±0.2 14.9 ± 0.2 16.1 ± 0.2 16.1 ± 0.2 17.8 ± 0.2 17.7 ± 0.2 16.8 ± 0.219.8 ± 0.2 20.8 ± 0.2 17.1 ± 0.2 21.7 ± 0.2 24.9 ± 0.2 20.7 ± 0.2 27.8 ±0.2 26.1 ± 0.2 21.3 ± 0.2 30.1 ± 0.2 30.8 ± 0.2 23.9 ± 0.2

Further manipulation of the MDU143 sample was performed and theresulting PXRD analyses are found in FIG. 4. The treatments involvedcalcination under air at 580° C., ozone-treatment at 150° C., TGAanalysis with ramping at 10° C.min⁻¹ under air and a Cu²⁺ exchange (viz.below). The material maintained most of its crystallinity in all cases,except in the TGA ramping procedure, where the sample was brought to900° C. The PXRD pattern of that treatment is indicative of a structuralcollapse and will be further discussed.

Example 2.2 Characterizations by Thermal Gravimetric Analysis (TGA)

The TGA analyses of an as-made Zn—Al-AEI is shown in FIG. 5, along witha calcined and ozone-treated version. The weight loss in the region of300-900° C. (with a distinct profile) in the case of the as-madematerial was attributed to the loss of the OSDA incorporated in thestructure from synthesis. The thermal weight profile of the calcined andozone-treated samples clearly showed that both methods efficientlyremoved the organic (and that water takes up some of the availablespace).

Beside weight loss information, the TGA analysis provided a reliable wayto assess the stability of materials. TGA can be a harsh thermaltreatment that can destroy microporous materials due to the hightemperatures reached (900° C.), as well as the fast ramping rate (10°C./min). As FIG. 4 already indicated, the as-made Zn—Al-AEI lost a greatdeal of its PXRD reflections and thus partially collapsed in TGA. Thiswas never seen for various control SSZ-39 samples, where all reflectionsremained with good intensities in PXRD following TGA. As straightforwardcomparison can be seen in FIG. 6 along with two additional controls: aZn²⁺-exchanged SSZ-39 (with a measured Zn/Al ratio of 0.3, obtained viaZn-nitrate exchange of a calcined MDU182) and a physical mixture ofas-made SSZ-39 and ZnO (15 wt %). In both controls, the PXRD visiblecrystallinity was totally preserved after TGA, indicative of the factthat the collapse of the Zn—Al-AEI material was not the collapse of aphysical mixture of SSZ-39 induced by the presence of extra-framework Znspecies. In other words, if the Zn—Al-AEI was either a physical mixtureof SSZ-39 (“aluminosilicate Al-AEI”) and ZnO or a Zn-exchanged SSZ-39,the structural collapse could not be explained. The collapse in TGA wasalso observed for the calcined and ozone-treated Zn—Al-AEI materials(not shown).

Example 2.3 Characterizations by Ion-Exchange Balance

Once having prepared these materials, there was an expectation that theion-exchange capacity (and especially for divalent cations such as Cu²⁺)would be higher for these zincoaluminosilicate matrices relative to thealuminosilicate analogs, especially given that both samples have asimilar Al content (Si/Al ratio). A complication with zinc species intetrahedral framework positions was the relative ease of theirhydrolysis and subsequent leaching in even slightly acidic media. It wasnoted that traditional ion-exchange methods affected the Si/Zn ratios(e.g. when 1M NH₄ ⁺-nitrate solutions were used, the Si/Zn ratio rosefrom 11.3 to 39.3 for calcined MDU143). Because of the increasinginsolubility of Cu²⁺ species at pH>6.5, a Schweizer's reagent(tetraaminediaquacopper dihydroxide) was used as ion-exchange medium.This provided a slightly basic way (pH around 9) to introduce Cu²⁺ tothe exchange sites and so protect the Zn sites from hydrolysis. Bycalcination, the ammonium ligands were then removed and the Si/Zn,Si/Al, and Cu/Al ratios were measured by EDS (Table 3) for an exchangedSSZ-39 and Zn—Al-AEI. A remarkable difference was found between SSZ-39and Zn—Al-AEI: the latter could exchange 0.35 Cu/Al (mol/mol), while theformer could only attain a 0.24 Cu/Al ratio. Even though some Zn seemedto be lost in the exchange (Si/Zn rose from 11 to 15), a 45% largerion-exchange capacity was thus found for the new material, stronglyindicative that at least a significant part of the Zn atoms are presentin the tetrahedral (alumino)siliceous AEI framework. Moreover, the highNa/Al ratio of the washed, calcined MDU143 material (Table 3) supportedthis conclusion: a high 1.8 value was obtained, whereas for classicSSZ-39 samples (not measured for MDU182), Na/Al values below 0.5 areusually obtained. In this case, alongwith the OSDA cation, Na⁺compensated part of the framework charge during synthesis.

TABLE 3 Composition of MDU182 and MDU143 after calcination, ion-exchangevia Schweizers reagent, and another calcination, compared to beforeexchange. before exchange after exchange synthesis type of material*Na/Al Si/Al Si/Zn Cu/Al Si/Al Si/Zn MDU182 Na⁺-SSZ-39 n.d. 8.0 / 0.247.5 / (Al-AEI) MDU143 Na⁺—Zn—Al-AEI 1.8 7.3 11.3 0.35 6.7 15.5 *Fromsynthesis, all framework negative charges that are not balanced by OSDAare compensated by Na⁺ due to the high Na content of the gels.

Example 2.4 Characterizations by ²⁹Si-NMR

The final and most direct proof for the present characterization was theobservation of additional Zn-derived signals in the ²⁹Si NMR spectra ofthe Zn—Al-AEI materials when compared to the Zn-free SSZ-39 (FIG. 7).Both materials had a similar Si/Al ratio (viz. Table 1, 2). The ratio ofthe signal of Si—(Si)₄— sites at −110 ppm and the Si—(Si)₃—(Al) sites at−105 ppm of about 2:1 in SSZ-39 was in line with its Si/Al ratio ofabout 8 of and the presence of mainly isolated Al sites in the siliceousmatrix. The calcined and ozone-treated Zn—Al-AEI materials displayed amuch higher signal at −105 ppm. This was likely due to the superpositionof both Si—(Si)₃—(Zn) and Si—(Si)₃—(Al) signals. The Si/Al ratio of thismaterial (7.7) could not have caused the −105 ppm signal to be nearly asintense as the -110 ppm signal. Additionally, in these new materials, asignal at −98 ppm was found, that was likely related to the presence ofsilanols [Si−(Si)₃—(OH)] in the material. This could for instance beenhanced by the presence of trifold tethered Zn in a siliceousenvironment, when one of the tetrahedral Zn—O—Si bond has beenhydrolyzed or did not form completely. Considering the ease ofhydrolysis demonstrated in the exchange experiments, this was likely. Tofurther support the present conclusion that the additional signals inthe Zn—Al-AEI derived from framework Zn, the ozone-treated Zn—Al AEImaterial was acid-treated, first in mild and then in harsh conditions(for conditions, see FIG. 7). The mild treatment did not remove much ofthe Zn from the framework as evidenced by the Si/Zn ratio of 19mentioned next to the NMR trace and the trace itself. After the harshtreatment, no Zn could be detected with EDS. And after calcination, the²⁹5i NMR spectra of the harsh treated one resembled that of the calcinedaluminosilicate SSZ-39. The crucial overlays of this Zn-free Zn—Al-AEIwith both the SSZ-39 and the Zn—Al-AEI are shown in FIG. 8. The PXRDtrace of this material was also identical to that of a calcined SSZ-39(not shown) and its reflections were stable after TGA analysis (notshown), confirming the removal of Zn and the creation of a type ofSSZ-39 from a Zn—Al-AEI by removing the framework Zn. This confirms thepresence of framework zinc in the starting material.

Example 2.4 Extension to Other Frameworks

The synthesis and properties of a novel zincoaluminosilicate having AEItopology is crystalline and isostructural with ALPO-18 and SSZ-39, as ithas a framework with the AEI topology (framework code of the structurecommission of the International Zeolite Association). To further extendthe methodology, the synthesis of zincoaluminosilicates with the GME andCHA topologies are also shown.

Entries 6 and 7 of Table 1 demonstrate the relative ease with which thesynthesis of Zn—Al-CHA and Zn—Al-GME was possible using similarsynthetic recipes with the right OSDA and adequate conditions. Thecorresponding PXRD traces of these materials can be found in FIG. 9 andmatch well with databases. For GME, an aluminosilicate control is given,with a Si/Al ratio of 4.1. Some of the reflections of the Zn—Al-GME wereclearly shifted towards lower 20 values (viz. dashed lines). Thisindicated that there was a measurable enhancement in certain dimensionsof the unit cell for the zincoaluminosilicate version of GME, aframework with 12MR 1-dimensional channels. This was expected given thelarger nature of Zn atoms and the higher level of heteroatom (Al+Zn)substitution in the zincoaluminosilicate framework.

Example 3 Final Comments

The totality of the available data support the conclusion that at leastpart of the Zn atoms in the Zn—Al-AEI material are present astetrahedral framework species in an aluminosilicate matrix. Based on theAEI, CHA and GME examples, it is also shown that thiszincoaluminosilicate synthesis method can be extended to other frameworktypes, especially for those topologies where aluminosilicatecompositions with high Al content are easily formed and morespecifically, for topologies that contain the d6r composite buildingblock (see International Zeolite Association, Database of ZeoliteStructures), seen in FIG. 1(B)). These two criteria are commondenominators for CHA, AEI and GME type materials.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present inventioncontemplates and claims those inventions resulting from the combinationof features of the invention cited herein and those of the cited priorart references which complement the features of the present invention.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis invention.

All of the references cited in this disclosure are incorporated byreference herein in their entireties for all purposes.

What is claimed:
 1. A process for preparing a zincoaluminosilicatecomposition, the process comprising hydrothermally treating an aqueouscomposition comprising: (a) a source of a silicon oxide, and optionallya source of germanium oxide or combination thereof; (b) a source ofaluminum oxide, and optionally a source of boron oxide, gallium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, zirconium oxide, or combination or mixture thereof; and(c) a source of a zinc oxide; (d) a mineralizing agent; and (e) anorganic structure directing agent (OSDA) comprising at least one isomerof the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of AEI or GME topology; wherein R^(A) andR^(B) are independently a C₁₋₃ alkyl, or together with the N to whichthey are bound form a 5 or 6 membered saturated or unsaturated ring; andR², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl;wherein the quaternary piperidinium cation has an associated bromide,chloride, fluoride, iodide, nitrate, or hydroxide anion.
 2. The processof claim 1, wherein the OSDA comprises at least one isomer of thequaternary piperidinium cation of Formula (IA) or (TB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl. In other Aspectsof this Embodiment, the quaternary piperidinium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.
 3. Theprocess of claim 1, wherein the quaternary piperidinium cation ofFormula (I) comprises an N,N-dialkyl-2,6-lupetidinium cation or anN,N-dialkyl-3,5-lupetidinium cation:


4. The process of claim 1, wherein the quaternary piperidinium cation ofFormula (I) comprises cis-N,N-dimethyl-3,5-lupetidinium cation,trans-N,N-dimethyl -3,5-lupetidinium cation, cis-N,N-dimethyl-2,6-lupetidinium cation, trans-N,N-dimethyl -2,6-lupetidinium cation ora combination thereof:

and the associated anion is hydroxide.
 5. A process for preparing azincoaluminosilicate composition of CHA topology, the process comprisinghydrothermally treating an aqueous composition comprising: (a) a sourceof a silicon oxide, and optionally a source of germanium oxide orcombination thereof; (b) a source of aluminum oxide, and optionally asource of boron oxide, gallium oxide, hafnium oxide, iron oxide, tinoxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, orcombination or mixture thereof; and (c) a source of a zinc oxide; (d) amineralizing agent; and (e) an organic structure directing agent (OSDA)comprising a trialkyladamantylammonium cation of Formula (II) or anoptionally substituted trialkylbenzylammonium cation of Formula (III):

under conditions effective to crystallize a crystalline microporouszincoaluminosilicate solid of CHA topology; wherein: R⁷, R⁸, and R⁹ areindependently C₁₋₆ alkyl or C₁₋₃ alkyl; and wherein the quaternarytrialkyladamantyl- or trialkylbenzyl-ammonium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion, andwherein the phenyl group of the trialkylbenzylammonium cation isoptionally substituted with one to three fluoro or optionallyfluorinated or perfluorinated C₁₋₃ alkyl groups.
 6. The process of claim5, wherein R⁷, R⁸, and R⁹ are each methyl.
 7. The process of claim 1,wherein the composition being hydrothermally treated comprises a sourceof silicon oxide, a source of aluminum oxide, and a source of zincoxide.
 8. The process of claim 1, wherein: (a) the source of siliconoxide is or comprises an aluminosilicate, a zincoaluminosilicate,zincosilicate a silicate, silica hydrogel, silicic acid, fumed silica,colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide orcombination thereof; (b) the source of aluminum oxide is or comprises analkoxide, hydroxide, or oxide of aluminum, a sodium aluminate, analuminum siloxide, an aluminosilicate, a zincoaluminosilicate,zincoaluminate or combination thereof; (c) the source of zinc oxide isor comprises a zinc(II) dicarboxylate, zinc(II) halide, zinc(II)hydroxide, zinc(II)oxide, zinc(II)nitrate, zincosilicate, zincoaluminateor zincoaluminosilicate.
 9. The process of claim 1, wherein the sourceof silicon oxide comprises sodium silicate, the source of Al comprises aFAU-zeolite, and the source of zinc oxide comprises zinc acetate. 10.The process of claim 1, wherein the mineralizing agent comprises anaqueous alkali metal or alkaline earth metal hydroxide.
 11. The processof claim 1, wherein: (a) the molar ratio of Al:Si is in a range of 0.005to 0.2. (b) the molar ratio of OSDA:Si is in a range of 0.1 to 0.75; (c)the molar ratio of water:Si is in a range of 5 to
 50. (d) the molarratio of total hydroxide:Si is in a range of 0.1 to 1.25; and (e) themolar ratio of Zn:Si is in a range of 0.01 to 0.2.
 12. The process ofclaim 1, wherein the conditions effective to crystallize a crystallinemicroporous zincoaluminosilicate solid of AEI, CHA, or GME topologyinclude treatment of the hydrothermally treated composition at atemperature in a range of from 100° C. to 200° C. for a time effectivefor crystallizing the crystalline microporous zincoaluminosilicatesolid.
 13. The process of claim 1, further comprising isolating thecrystalline microporous zincoaluminosilicate solid.
 14. The process ofclaim 13, further comprising the steps of: (a) heating the isolatedcrystalline microporous zincoaluminosilicate solid at a temperature in arange of from about 250° C. to about 600° C.; or (b) contacting theisolated crystalline microporous zincoaluminosilicate solid with ozoneor other oxidizing agent at a temperature in a range of 100° C. to 200°C.; or (c) heating the isolated crystalline microporouszincoaluminosilicate solid at a temperature in a range of from about200° C. to about 600° C. in the presence of an alkali, alkaline earth,transition metal, rare earth metal, ammonium or alkylammonium salt; fora time sufficicient to form a dehydrated or an OSDA-depleted product.15. The process of claim 14, further comprising treating the dehydratedor OSDA-depleted product with an aqueous ammonium or metal cation salt.16. The process of claim 14, further comprising treating at least somepores of the calcined crystalline microporous zincoaluminosilicate solidwith at least one type of transition metal or transition metal oxide.17. A composition comprising: (a) a source of a silicon oxide, andoptionally a source of germanium oxide, or combination thereof; (b) asource of aluminum oxide, and optionally a source of boron oxide,gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide,indium oxide, vanadium oxide, zirconium oxide, or combination or mixturethereof; and (c) a source zinc oxide; (d) a mineralizing agent; (e) anorganic structure directing agent (OSDA) comprising at least one isomerof the quaternary piperidinium cation of Formula (I):

and (f) a compositionally consistent crystalline microporouszincoaluminosilicate solid of an AEI or GME topology; wherein R^(A) andR^(B) are independently a C₁₋₃ alkyl, or together with the N to whichthey are bound form a 5 or 6 membered saturated or unsaturated ring; andR², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃ alkyl, provided atleast two of R², R³, R⁴, R⁵, and R⁶ are independently C₁₋₃ alkyl; andwherein the quaternary piperidinium cation has an associated bromide,chloride, fluoride, iodide, nitrate, or hydroxide anion.
 18. Thecomposition of claim 17, wherein, the OSDA comprises at least one isomerof the quaternary piperidinium cation of Formula (IA) or (TB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl.
 19. Thecomposition of claim 17, wherein the quaternary piperidinium cation ofFormula (I) is an N,N-dialkyl-2,6-lupetidinium cation orN,N-dialkyl-3,5-lupetidinium cation:


20. The composition of claim 17, wherein the quaternary piperidiniumcation of Formula (I) is cis-N,N-dimethyl-3,5-lupetidinium cation.
 21. Acomposition comprising: (a) a source of a silicon oxide, and optionallya source of germanium oxide or combination thereof; (b) a source ofaluminum oxide, and optionally a source of boron oxide, gallium oxide,hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide,vanadium oxide, zirconium oxide, or combination or mixture thereof; and(c) a source of a zinc oxide; (d) a mineralizing agent; (e) an organicstructure directing agent (OSDA) comprising a trialkyladamantylammoniumcation of Formula (II) or an optionally substitutedtrialkylbenzylammonium cation of Formula (III):

and (f) a compositionally consistent crystalline microporouszincoaluminosilicate solid of a CHA topology wherein: R⁷, R⁸, and R⁹ areindependently C₁₋₆ alkyl or C₁₋₃ alkyl; and wherein the quaternarytrialkyladamantyl- or trialkylbenzyl-ammonium cation has an associatedbromide, chloride, fluoride, iodide, nitrate, or hydroxide anion. 22.The composition of claim 21, wherein R⁷, R⁸, or R⁹ are all methyl. 23.The composition of claim 21, wherein the associated anion is hydroxide.24. The composition of claim 17, wherein the optionally sources ofgermanium oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, indium oxide, vanadium oxide, or zirconiumoxide are absent.
 25. The composition of claim 17, wherein: (a) thesource of silicon oxide comprises an aluminosilicate, azincoaluminosilicate, zincosilicate a silicate, silica hydrogel, silicicacid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, asilica hydroxide or combination thereof; (b) the source of aluminumoxide comprises an alkoxide, hydroxide, or oxide of aluminum, a sodiumaluminate, an aluminum siloxide, an aluminosilicate, azincoaluminosilicate, zincoaluminate or combination thereof; (c) thesource of zinc oxide comprises a zinc(II) dicarboxylate, zinc(II)halide, zinc(II) hydroxide, zinc(II)oxide, zinc(II)nitrate,zincosilicate, zincoaluminate or zincoaluminosilicate.
 26. Thecomposition of claim 17, wherein the source of silicon oxide comprisessodium silicate, the source of Al comprises a FAU-zeolite, and thesource of zinc oxide comprises zinc acetate.
 27. The composition ofclaim 17, wherein one of the sources of each of the silicon oxide, thezinc oxide, and aluminum oxide comprises a Zn—Al-containing FAUmolecular sieve.
 28. The composition of claim 17, wherein themineralizing agent comprises an aqueous alkali metal or alkaline earthmetal hydroxide.
 29. The composition of claim 17, wherein: (a) the molarratio of Al:Si is in a range of from 0.005 to 0.2; (b) the molar ratioof OSDA:Si is in a range of from 0.1 to 0.75; (c) the molar ratio ofwater:Si is in a range of from 5 to 50; (d) the molar ratio of totalhydroxide:Si is in a range of from 0.1 to 1.25; and (e) the molar ratioof Zn:Si is in a range of from 0.01 to 0.2.
 30. The composition of claim17, that is a gel.
 31. A crystalline microporous zincoaluminosilicatesolid of GME or AEI topology having pores at least some of which areoccluded with quaternary piperidinium cations of Formula (I):

wherein R^(A) and R^(B) are independently a C₁₋₃ alkyl, or together withthe N to which they are bound form a 5 or 6 membered saturated orunsaturated ring; and R², R³, R⁴, R⁵, and R⁶ are independently H or C₁₋₃alkyl, provided at least two of R², R³, R⁴, R⁵, and R⁶ are independentlyC₁₋₃ alkyl.
 32. A crystalline microporous zincoaluminosilicate solid ofAEI or GME topology, wherein the OSDA comprises at least one isomer ofthe quaternary piperidinium cation of Formula (IA) or (TB):

wherein R² R³, R⁵, and R⁶ are independently C₁₋₃ alkyl.
 33. Thecrystalline microporous zincoaluminosilicate solid of claim 32, whereinthe OSDA comprises s an N,N-dialkyl-2,6-lupetidinium cation orN,N-dialkyl-3,5-lupetidinium cation:


34. The crystalline microporous zincoaluminosilicate solid of claim 32,wherein the quaternary piperidinium cation of Formula (I) comprises acis-N,N-dimethyl-3,5-lupetidinium cation,trans-N,N-dimethyl-3,5-lupetidinium cation,cis-N,N-dimethyl-2,6-lupetidinium cation,trans-N,N-dimethyl-2,6-lupetidinium cation or a combination thereof. 35.A crystalline microporous zincoaluminosilicate solid of CHA topologyhaving pores at least some of which are occluded with atrialkyladamantylammonium cation of Formula (II) or an optionallysubstituted trialkylbenzylammonium cation of Formula (III):

wherein: R⁷, R⁸, and R⁹ are independently C₁₋₆ alkyl or C₁₋₃ alkyl;wherein the quaternary trialkyladamantyl- or trialkylbenzyl-ammoniumcation has an associated bromide, chloride, fluoride, iodide, nitrate orhydroxide anion; and wherein the phenyl group of thetrialkylbenzylammonium cation is optionally substituted with one tothree fluoro or optionally fluorinated or perfluorinated C₁₋₃ alkylgroups.
 36. The crystalline microporous zincoaluminosilicate solid ofclaim 35, wherein R⁷, R⁸, or R⁹ are all methyl.
 37. A crystallinemicroporous zincoaluminosilicate solid having an AEI, CHA, or GMEtopology.
 38. The crystalline microporous zincoaluminosilicate solid ofclaim 37, having AEI or GME topology and a molar ratio of Si:Al in arange of from 3 to about 200 (or SiO₂/Al₂O₃ ratio of from 6 to 400) andmolar ratio of Si:Zn in a range from 5 to
 50. 39. The crystallinemicroporous zincoaluminosilicate solid of claim 35, having a CHAtopology and a molar ratio of Si:Al in a range of from 4 to 100 (orSiO₂/Al₂O₃ ratio from 8 to 200) and molar ratio of Si:Zn in a range from5 to
 50. 40. The crystalline microporous zincoaluminosilicate solid ofclaim 37, exhibiting at least one of the following: (a) an XRD patternthe same as or consistent with any one of those shown in FIG. 3(Zn—Al-AEI), FIG. 4 (Zn—Al-AEI), or FIG. 9 (Zn—Al-GME and Zn—Al-CHA);(b) an XRD pattern having at least the five major peaks substantially asprovided in Table
 2. (c) an ²⁹Si MAS spectrum for having a plurality ofchemical shifts of about −110.5, −105, −99.5 ppm downfield of a peakcorresponding to and external standard of tetramethylsilane (forZn—Al-AEI); or (d) an ²⁹Si MAS spectrum the same as or consistent withthe one shown in FIG. 8 for Zn—Al-AEI.
 41. The crystalline microporouszincoaluminosilicate solid of claim 37, comprising pores, at least someof which contain: (a) Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In,Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, orR_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4; or (b) scandium,yttrium, titanium, tin, zirconium, vanadium, manganese, chromium,molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium,nickel, palladium, platinum, copper, silver, gold, or mixtures thereof,each as a metal, oxide, or salt.
 42. A process comprising carbonylatingDME with CO at low temperatures, reducing NOx with methane, reducing NOxwith ammonia, converting methane via partial oxidation to methanol,converting a lower alcohol or other oxygenated product to at least onetype of olefin, cracking, dehydrogenating, converting paraffins toaromatics, MTO, isomerizing xylenes, disproportionating toluene,alkylating aromatic hydrocarbons, oligomerizing alkenes, aminating loweralcohols, separating and sorbing lower alkanes, hydrocracking ahydrocarbon, dewaxing a hydrocarbon feedstock, isomerizing an olefin,producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon, reforming a hydrocarbon, converting a lower alcoholor other oxygenated hydrocarbon to produce an olefin products, reducingthe content of an oxide of nitrogen contained in a gas stream in thepresence of oxygen, or separating nitrogen from a nitrogen-containinggas mixture by contacting the respective feedstock with a catalystcomprising the crystalline microporous zincoaluminosilicate solid ofclaim 37 under conditions sufficient to affect the named transformation.43. The process of claim 42, comprising reducing NOx in exhaust gases bycatalytic reduction (e.g., with ammonia) or converting methane viapartial oxidation to methanol, for examples with O₂, H₂O₂, or N₂O, witha catalyst comprising a copper exchanged crystalline microporouszincoaluminosilicate solid of AEI or CHA topology, under conditionssufficient to affect the named transformation.
 44. The process of claim42, comprising converting a lower alcohol or other oxygenated product toat least one type of olefin with the catalyst under conditionssufficient to affect the named transformation.
 45. An ion exchangematerial comprising the crystalline microporous zincoaluminosilicatesolid claim 37.